CN104321486A

CN104321486A - Wet lap composition and related processes

Info

Publication number: CN104321486A
Application number: CN201180050648.4A
Authority: CN
Inventors: R.K.古普塔; M.G.米切尔; D.W.克罗西维奇; M.D.克拉克; C.D.安德森; M.L.米切尔; P.H.米切尔; A.L.沃尔夫
Original assignee: Eastman Chemical Co
Current assignee: Eastman Chemical Co
Priority date: 2010-10-21
Filing date: 2011-10-20
Publication date: 2015-01-28
Also published as: EP2630297A1; US20110139386A1; WO2012054674A1; EP2630297B1; JP2013540212A; BR112013009684A2; KR20130132442A; EP2630297A4

Abstract

A microfiber-containing wet lap composition is provided. The wet lap composition comprises a mixture of a sulfopolyester dispersion and a plurality of water nondispersible synthetic polymer microfibers. The microfibers have an equivalent diameter of less than 5 microns and a length of less than 25 millimeters. The sulfopolyester dispersion comprises at least one sulfopolyester and water.

Description

Wet lapped composition and related process

The cross reference of related application

The application is part subsequent application, require the patent application serial numbers 12/199 enjoying application on August 27th, 2008, the benefit of priority of 304, the latter is the provisional application Ser.No 61/041 of application on April 2nd, 2008, the patent application serial numbers 11/648 of the part subsequent application of 699 and application on January 3rd, 2007, the part subsequent application of 955, the latter is again the patent application serial numbers 11/344 of application on January 31st, 2006, the part subsequent application of 320, the latter is the patent application serial numbers 11/204 of application on August 16th, 2005, the part subsequent application of 868, the latter is the patent application serial numbers 10/850 of application on May 20th, 2004, 548(authorizes as U.S. Patent number 6 now, 989, 193) division, the latter is the patent application serial numbers 10/465 of application on June 19th, 2003, the part subsequent application of 698.Aforementioned application is incorporated herein by this reference.

Invention field

The application relates to the water-dispersible fiber and fibre that comprise sulfonic polyester.The invention further relates to the multicomponent fibre and fine-denier fiber prepared therefrom and fibre that comprise sulfonic polyester.The invention still further relates to the technique for water dispersible multicomponent fine-denier fiber and bondedfibre fabric prepared therefrom.This fiber and fibre can be used in flushable personal care product and medical product.

Background of invention

Fiber, meltblown fiber web and other melt-spun fibre goods are prepared by thermoplastic polymer (such as polypropylene, polyamide and polyester).A kind of common application of these fibers and fibre is bondedfibre fabric; particularly such as wipe paper, feminine hygiene products, baby diaper, adult incontinent briefs, hospital/operation and other disposable medical articles for use, textile protection and layer, geotextile, industrial wipes personal care product, and in filter medium.Regrettably, the personal care product be made up of conventional thermoplastic's polymer is difficult to dispose, and is usually placed in landfill waste.A kind of promising alternative method of disposal makes these products or other assemblies " flushable ", can be compatible with public sewerage.The use of water dispersible or water miscible material also improves reusable edible and the recyclability of personal care product.Various thermoplastic polymers itself used in current personal care product do not have water dispersible or water-soluble, therefore can not prepare and easily decompose and can throw aside in sewage disposal system or the goods of easily recycle.

The demand of flushable personal care product is caused to the fiber of the water-responsive degree needing to have various degree, non-woven material and other fibres.Describe the various methods solving these demands, such as, at U.S. Patent number 6,548,592,6,552,162,5,281,306,5,292,581,5,935,880 and 5,509,913; U.S. Patent Application Serial Number 09/775,312 and 09/752,017; With in PCT International Publication WO 01/66666 A2.But these methods all encounter shortcomings, and the fibre with gratifying performance characteristics balance (such as TENSILE STRENGTH, absorbability, pliability and the web integrity under dry wet two kinds of conditions) can not be provided, such as fiber or bondedfibre fabric.

Such as, typical non-woven technology has strong globality and the net of character needed for other based on the fiber of multidirectional deposition resin-bonded adhesive treatment to be formed.But the sub-assembly obtained usually has poor water-responsive and is unsuitable for flushable application.The existence of adhesive also may cause inapt character in the final product, the rising of the reduction of such as sheet material wettability, the rising of hardness, viscosity and production cost.And be difficult to prepare in use demonstrate enough wet strength simultaneously still can when throwing aside the adhesive of rapid dispersion.Therefore, use the nonwoven sub-assembly of these adhesives may decompose at ambient conditions slowly, or under body fluid exists, there is not enough wet strength properties.In order to address this problem, be known to the water-dispersible adhesive (such as there is or do not have the latex comprising acrylic or methacrylic acid of outside heating) of pH value and ion-sensitive, and being described in such as U.S. Patent number 6,548, in 592 B1.But the ion concentration in public sewage and house rot system and pH value level can vary widely between each geographical position, and may be not enough to make adhesive become solvable and dispersible.In this case, after throwing aside, fibre also can not decompose, and can block drainpipe or sewage branch line.

Such as at U.S. Patent number 5,916,678,5,405,698,4,966,808,5,525,282,5,366,804,5,486, describe the multicomponent fibre comprising water dispersible compositions and thermoplasticity nonaqueous dispersion component in 418.Such as, these multicomponent fibres can be the bicomponent fibers with shaping or the cross section (such as fabric of island-in-sea type, core-skin type, parallel type or segmented pie configurations) through design.This multicomponent fibre can be passed through water or dilute alkaline soln process, and wherein water dispersible compositions dissolves and leaves nonaqueous dispersion component as the very little individual fibers of separating of fineness.But the polymer with superior water dispersibility can give obtained multicomponent fibre viscosity usually, and this can cause fiber to be bonded together, to lump or to fuse in winding process or after storing several days, especially under moistening hot conditions.In order to prevent fusion, usually apply the finishing agent based on aliphatic acid or oil at fiber surface.In addition, in aqueous dispersion polymers, the pigment of vast scale or filler is sometimes also added to prevent the fusion of fiber, as such as U.S. Patent number 6,171, described in 685.This oil dressing agent, pigment and filler need other treatment step, and can give final fiber inapt character.A lot of aqueous dispersion polymers also needs aqueous slkali to be removed, and this can cause the degeneration of other polymers compositionss of fiber, such as the reduction of inherent viscosity, toughness and melt strength.In addition, some aqueous dispersion polymers can not tolerate and be exposed to water in hydroentanglement procedure, and are therefore unsuitable for preparing nonwoven web and fabric.

Selectively, water dispersible compositions can serve as the adhesive of thermoplastic fibre in nonwoven web.Once be exposed to water, the combination between fiber with fiber separates, and makes nonwoven web lose its globality and resolves into independent fiber.But the thermoplastic polymer component of these nonwoven webs is not water dispersible and is still present in water-bearing media, therefore finally must remove from municipal wastewater treatment apparatus.Can use and Hydroentangledly prepare decomposable bondedfibre fabric, this fabric uses or does not use the added binding agents of very low amount (<5wt%) to be combined by fiber.Although these fabrics throw aside rear decomposable asymmetric choice net, their use fiber that is water-insoluble or nonaqueous dispersion usually, and may cause and tangle and blocking in sewerage.Any external adding water dispersion glues is subject to Hydroentangled impact and also must minimizes and can not form gel aggregation or cross-linking agent, thus is of value to the relevant problem of fabric treating or sewage.

Can obtain several water-soluble or aqueous dispersion polymers, but they are not suitable for meltblown fibers preparation manipulation or melt spinning usually.Polymer such as polyvinyl alcohol, polyvinylpyrrolidone and polyacrylic acid are not melt-processable, because the temperature that they are reaching below the temperature spot of applicable melt viscosity thermal decomposition will occur.Polyethylene Oxide with High-mole cular-weight may have applicable heat endurance, but can provide full-bodied solution at polymer interface place, causes the speed of decomposition slow.Water dispersible sulfonic polyester has been described in such as U.S. Patent number 6,171,685,5,543,488,5,853,701,4,304,901,6,211,309,5,570,605,6,428,900 and 3,779, in 993.But typical sulfonic polyester is low molecular weight thermoplastic, that it is fragility and lack and bear operating winding and do not rupture or the pliability of flexible material webs to produce.Sulfonic polyester also can show caking or fusion in the process of processing film forming or fiber, and this may need to use oil dressing agent or a large amount of pigment or filler to be avoided.Low molecular weight polyethylene glycol oxide (being more generally called polyethylene glycol) is the polymer of insecure/fragility, and it does not have the physical property needed for fiber applications yet.Preparing fiber by known water-soluble polymer through solution technique is candidate materials, but the complexity that removal solvent (especially water) increases improves production cost.

Therefore, need water-dispersible fiber and fibre prepared therefrom, its in the presence of moisture (when being especially exposed to human body fluid) there is enough TENSILE STRENGTH, absorbability, pliability and fabric integrity.In addition, need following fibre, it does not need adhesive and can be dispersed or dissolved in completely in house or domestic sewerage systems.Potential purposes includes but not limited to: meltblown fiber web, nonwoven fabric, Hydroentangled fabric, wet laid nonwoven material, dry-laying non-woven material, bicomponent fiber component, adhesion-promoting layer, for cellulosic adhesive, flushable non-woven material and film, soluble binding agent fiber, protective layer and for be released or be dissolved in the carrier of the active component in water.Also need the multicomponent fibre with water dispersible compositions, this fiber does not demonstrate excessive long filament caking or fusion in spinning operations, is easy to the hot water removing with neutral or faintly acid pH value, and is suitable for preparing bondedfibre fabric by hydroentanglement processes.These multicomponent fibres can be used in preparing the microfiber that can be used for preparing various goods.Other are extrudable is also possible with melt-spun fibre material.

Summary of the invention

We are surprised to find that and can prepare pliable and tough water-dispersible fiber by sulfonic polyester.Therefore the invention provides water-dispersible fiber, it comprises:

(A) have the sulfonic polyester of the glass transition temperature (Tg) of at least 25 DEG C, this sulfonic polyester comprises:

The residue of (i) one or more dicarboxylic acids;

(ii) with the total amount of repetitive, the residue of at least one sulfomonomer of about 4 to about 40 % by mole, this monomer has 2 functional groups and one or more sulfonate groups be connected on aromatics or cyclic aliphatic ring, and wherein said functional group is hydroxyl, carboxyl or their combination;

(iii) one or more diol residue, wherein with the total amount of diol residue, at least 25 % by mole is the polyethylene glycol with following structure:

Wherein n is the integer in 2 to about 500 scopes; With

(iv) with the total amount of repetitive, the residue with the branched monomer of 3 or more functional groups of 0 to about 25 % by mole, wherein said functional group is hydroxyl, carboxyl or their combination;

(B) the optional aqueous dispersion polymers blended with described sulfonic polyester; With

(C) the optional nonaqueous dispersion polymer blended with described sulfonic polyester, condition is this blend is immiscible blend;

Wherein with the total weight of fiber, this fiber comprises the pigment or filler that are less than 10wt%.

Fiber of the present invention can be homofil, its rapid dispersion or dissolving and can by melt jet or melt spinning preparation in water.This fiber can be only made up of sulfonic polyester or be made up of the blend of sulfonic polyester and water dispersible or nonaqueous dispersion polymer.Therefore, fiber of the present invention optionally can comprise the aqueous dispersion polymers blended with sulfonic polyester.In addition, this fiber optionally can comprise the nonaqueous dispersion polymer blended with sulfonic polyester, and condition is this blend is immiscible blend.The present invention also comprises the fibre comprising water-dispersible fiber of the present invention.Therefore, fiber of the present invention may be used for preparing various fibre, such as yarn, meltblown fiber web, spun-bonded fibre net and bondedfibre fabric, they because of but water dispersible or flushable.Staple fibre of the present invention also can with natural in paper, nonwoven web and weaving yarn or synthetic fiber be blended.

Another aspect of the present invention is water-dispersible fiber, and it comprises:

(i) with the total amount of sour residue, one or more M-phthalic acids of about 50 to about 96 % by mole or the residue of terephthalic acid (TPA);

(ii) with the total amount of sour residue, the sodium of about 4 to about 30 % by mole is for the residue of sulfoisophthalic acid;

Wherein n is the integer in 2 to about 500 scopes;

(iv) with the total amount of repetitive, the residue with the branched monomer of 3 or more functional groups of 0 to about 20 % by mole, wherein said functional group is hydroxyl, carboxyl or their combination;

(B) optional first aqueous dispersion polymers blended with described sulfonic polyester; With

(C) nonaqueous dispersion polymer that is optional and the blended formation blend of described sulfonic polyester, condition is this blend is immiscible blend;

Water-dispersible fiber goods of the present invention comprise personal care product, such as, wipe paper, gauze, chiffon, diaper, training pant, female sanitary towel, bandage, wound care thing and operation dressing.Except having water dispersible, fibre of the present invention or flushable, can be compatible with domestic sewerage systems and be suitable for throwing aside wherein with house.

Present invention also offers the multicomponent fibre comprising water dispersible sulfonic polyester and one or more nonaqueous dispersion polymer.The geometry that this fiber has through design makes nonaqueous dispersion polymer exist as fragment, and described fragment is namely between middle sulfonic polyester and fully keeps apart each other, and this sulfonic polyester serves as adhesive or the encapsulation matrix of nonaqueous dispersion fragment.Therefore, another aspect of the present invention is the multicomponent fibre with shaping cross section, comprises:

(A) have the water dispersible sulfonic polyester of the glass transition temperature (Tg) of at least 57 DEG C, this sulfonic polyester comprises:

The residue of (i) one or more dicarboxylic acids;

(ii) with the total amount of repetitive, the residue of at least one sulfomonomer of about 4 to about 40 % by mole, this sulfomonomer has 2 functional groups and one or more sulfonate groups be connected on aromatics or cyclic aliphatic ring, and wherein said functional group is hydroxyl, carboxyl or their combination;

Wherein n is the integer in 2 to about 500 scopes;

(iv) with the total amount of repetitive, the residue with the branched monomer of 3 or more functional groups of 0 to about 25 % by mole, wherein said functional group is hydroxyl, carboxyl or their combination; With

(B) multiple fragment, it comprises one or more and the immiscible nonaqueous dispersion polymer of described sulfonic polyester, and the described sulfonic polyester that wherein said fragment is namely between fragment is fully kept apart each other;

This sulfonic polyester has the glass transition temperature of at least 57 DEG C, and it greatly reduces caking and the fusion of fiber during winding and long term storage.

Sulfonic polyester can be removed by making described multicomponent fibre contact with water, leaving nonaqueous dispersion fragment as fine-denier fiber.Therefore present invention also offers the technique for fine-denier fiber, comprising:

(A) the water dispersible sulfonic polyester of the glass transition temperature (Tg) with at least 57 DEG C is spun to multicomponent fibre with one or more and this immiscible nonaqueous dispersion polymer of sulfonic polyester, described sulfonic polyester comprises:

Wherein n is the integer in 2 to about 500 scopes; With

Wherein said fiber has multiple fragment comprising described nonaqueous dispersion polymer, and the described sulfonic polyester that wherein said fragment is namely between fragment is fully kept apart each other; And with the total weight of fiber, this fiber comprises the pigment or filler that are less than 10wt%; And

(B) make described multicomponent fibre contact with water to remove described sulfonic polyester, thus form fine-denier fiber.

Described nonaqueous dispersion polymer can be biodegradable according to DIN Standard 54900 mensuration and/or measure according to ASTM standard method D6340-98 is biodegradable.Described multicomponent fibre for the preparation of fibre such as yarn, fabric, meltblown fiber web, spun-bonded fibre net or bondedfibre fabric, and can also can comprise one or more fibrage.Thus the described fibre with multicomponent fibre can contact the fibre producing and comprise fine-denier fiber with water.

Therefore, another aspect of the present invention is the technique for fine-denier fiber net, comprising:

(A) the water dispersible sulfonic polyester of the glass transition temperature (Tg) with at least 57 DEG C is spun to multicomponent fibre with one or more and this immiscible nonaqueous dispersion polymer of sulfonic polyester, this sulfonic polyester comprises:

Wherein n is the integer in 2 to about 500 scopes; With

Wherein said multicomponent fibre has multiple fragment comprising described nonaqueous dispersion polymer, and the described sulfonic polyester that wherein said fragment is namely between fragment is fully kept apart each other; And with the total weight of described fiber, this fiber comprises the pigment or filler that are less than 10wt%;

(B) overlapping for the multicomponent fibre of steps A and collection are formed nonwoven web; And

(C) make this nonwoven web contact with water to remove described sulfonic polyester, thus form fine-denier fiber net.

The present invention also provides the technique preparing water dispersible bondedfibre fabric, comprising:

(A) water-dispersity polymer composite is heated to the temperature of more than its flow point, wherein this polymer composition comprises:

I () has the sulfonic polyester of the glass transition temperature (Tg) of at least 25 DEG C, this sulfonic polyester comprises:

The residue of (a) one or more dicarboxylic acids;

B () is with the total amount of repetitive, the residue of at least one sulfomonomer of about 4 to about 40 % by mole, this sulfomonomer has 2 functional groups and one or more metal sulfonate salt group be connected on aromatics or cyclic aliphatic ring, and wherein said functional group is hydroxyl, carboxyl or their combination;

(c) one or more diol residue, wherein with the total amount of diol residue, at least 20 % by mole is the polyethylene glycol with following structure:

Wherein n is the integer in 2 to about 500 scopes;

(d) with the total amount of repetitive, the residue with the branched monomer of 3 or more functional groups of 0 to about 25 % by mole, wherein said functional group is hydroxyl, carboxyl or their combination;

(ii) the optional aqueous dispersion polymers blended with described sulfonic polyester; With

(iii) nonaqueous dispersion polymer that is optional and the blended formation blend of described sulfonic polyester, condition is this blend is immiscible blend;

Wherein with the total weight of polymer composition, described polymer composition comprises the pigment or filler that are less than 10wt%;

(B) melt spinning becomes long filament; With

(C) overlapping and collect the long filament of step B to form nonwoven web.

In another aspect of this invention, provide the multicomponent fibre with shaping cross section, comprise:

(A) at least one water dispersible sulfonic polyester; With

(B) multiple microfiber territory comprising one or more and the immiscible nonaqueous dispersion polymer of described sulfonic polyester, the described sulfonic polyester that wherein said territory is namely between territory is fully kept apart each other,

Wherein said fiber have be less than about 6 dawn/long filament be spun into denier;

Wherein said water dispersible sulfonic polyester demonstrates the melt viscosity being less than about 12000 pools recorded with the strain rate of 1 rad/sec at 240 DEG C, and wherein in the total mole number of diacid or diol residue, described sulfonic polyester comprises the residue of at least one sulfomonomer being less than about 25 % by mole.

In another aspect of this invention, provide the multicomponent extrudate with shaping cross section, comprise:

(A) at least one water dispersible sulfonic polyester; With

(B) multiple territory comprising one or more and the immiscible nonaqueous dispersion polymer of described sulfonic polyester, the described sulfonic polyester that wherein said territory is namely between territory is fully kept apart each other, and wherein said extrudate can with the speed fusion drawn at least about 2000m/min.

In another aspect of this invention, provide the technique for the preparation of the multicomponent fibre with shaping cross section, comprise: by least one water dispersible sulfonic polyester and one or more and this sulfonic polyester immiscible nonaqueous dispersion polymer spinning, wherein said multicomponent fibre has multiple territory comprising described nonaqueous dispersion polymer, and the described sulfonic polyester that described territory is namely between territory is fully kept apart each other; Wherein said multicomponent fibre have be less than about 6 dawn/long filament be spun into denier; Wherein said nonaqueous dispersion sulfonic polyester demonstrates the melt viscosity being less than about 12000 pools recorded with the strain rate of 1 rad/sec at 240 DEG C; And wherein in the total mole number of diacid or diol residue, described sulfonic polyester comprises the residue of at least one sulfomonomer being less than about 25 % by mole.

In another aspect of this invention, provide the technique for the preparation of the multicomponent fibre with shaping cross section, comprise: by least one water dispersible sulfonic polyester and one or more and this immiscible nonaqueous dispersion of sulfonic polyester polymer-extruded to prepare multicomponent extrudate, wherein this multicomponent extrudate has multiple territory comprising described nonaqueous dispersion polymer, and the described sulfonic polyester that described territory is namely between territory is fully kept apart each other; With with multicomponent extrudate described in the speed fusion drawn at least about 2000m/min.

On the other hand, the invention provides the technique for the preparation of fine-denier fiber, comprising:

(A) at least one water dispersible sulfonic polyester and one or more and this immiscible nonaqueous dispersion polymer of sulfonic polyester are spun to multicomponent fibre, wherein said multicomponent fibre has multiple territory comprising described nonaqueous dispersion polymer, and the described sulfonic polyester that wherein said territory is namely between territory is fully kept apart each other; Wherein said multicomponent fibre have be less than about 6 dawn/long filament be spun into denier; Wherein said nonaqueous dispersion sulfonic polyester demonstrates the melt viscosity being less than about 12000 pools recorded with the strain rate of 1 rad/sec at 240 DEG C; And wherein in the total mole number of diacid or diol residue, described sulfonic polyester comprises the residue of at least one sulfomonomer being less than about 25 % by mole; And

(B) make described multicomponent fibre contact with water to remove described water dispersible sulfonic polyester, thus form the fine-denier fiber of one or more nonaqueous dispersion polymer described.

(A) by least one water dispersible sulfonic polyester and one or more and this immiscible nonaqueous dispersion of sulfonic polyester polymer-extruded to prepare multicomponent extrudate, wherein said multicomponent extrudate has multiple territory comprising described nonaqueous dispersion polymer, and the described sulfonic polyester that wherein said territory is namely between territory is fully kept apart each other;

(B) with multicomponent extrudate described in the speed fusion drawn at least about 2000m/min to form multicomponent fibre; And

(C) make this multicomponent fibre contact with water to remove described water dispersible sulfonic polyester, thus form the fine-denier fiber of one or more nonaqueous dispersion polymer described.

In another aspect of this invention, provide the technique for the preparation of fine-denier fiber net, comprising:

(A) at least one water dispersible sulfonic polyester and one or more and this immiscible nonaqueous dispersion polymer of sulfonic polyester are spun to multicomponent fibre, described multicomponent fibre has multiple territory comprising described nonaqueous dispersion polymer, and the described water dispersible sulfonic polyester that wherein said territory is namely between territory is fully kept apart each other; Wherein said multicomponent fibre have be less than about 6 dawn/long filament be spun into denier; Wherein said nonaqueous dispersion sulfonic polyester demonstrates the melt viscosity being less than about 12000 pools recorded with the strain rate of 1 rad/sec at 240 DEG C; And wherein in the total mole number of diacid or diol residue, described sulfonic polyester comprises the residue of at least one sulfomonomer being less than about 25 % by mole;

(B) multicomponent fibre of step (A) is collected to form nonwoven web; And

(C) make this nonwoven web contact with water to remove described water dispersible sulfonic polyester, thus form fine-denier fiber net.

In another aspect of this invention, provide the technique for the preparation of micro Denier net, comprising:

(A) by least one water dispersible sulfonic polyester and one or more and this immiscible nonaqueous dispersion of sulfonic polyester polymer-extruded to prepare multicomponent extrudate, described multicomponent extrudate has multiple territory comprising described nonaqueous dispersion polymer, and the described sulfonic polyester that wherein said territory is namely between territory is fully kept apart each other;

(C) multicomponent fibre of step (B) is collected to form nonwoven web; And

(D) make this nonwoven web contact with water to remove described sulfonic polyester, thus form fine-denier fiber net.

In another embodiment of the present invention, provide the technique for the preparation of nonaqueous dispersion polymer microfibers, described technique comprises:

A) multicomponent fibre is cut into short multicomponent fibre of cutting;

B) fibrous raw material is made to contact to prepare fiber-incorporated slurry with water; Wherein said fibrous raw material packet cuts multicomponent fibre containing short;

C) this fiber-incorporated slurry is heated with the fiber-incorporated slurry of preparation through heating;

D) optionally, in shear zone, described fiber-incorporated slurry is mixed;

E) from described multicomponent fibre, remove described sulfonic polyester at least partially comprise the slurry mix of sulfopolyester dispersion and nonaqueous dispersion polymer microfibers with preparation; And

F) from this slurry mix, described nonaqueous dispersion polymer microfibers is isolated.

In another embodiment of the present invention, provide the described nonaqueous dispersion polymer microfibers comprising at least one nonaqueous dispersion polymer, wherein said nonaqueous dispersion polymer microfibers has the equivalent diameter being less than 5 microns and the length being less than 25 millimeters.

In another embodiment of the present invention, provide the technique for being prepared nonwoven articles by described nonaqueous dispersion polymer microfibers, described technique comprises:

A) the nonaqueous dispersion polymer microfibers prepared by multicomponent fibre is provided; And

B) wet laying process or dry-laying process is used to prepare nonwoven articles.

Accompanying drawing is sketched

Fig. 1 a, 1b and 1c are the viewgraph of cross-section of three kinds of heteroid fibers, especially exemplified with the assay method of each measured value of size and dimension relating to fiber.

Detailed Description Of The Invention

The invention provides (when being especially exposed to human body fluid) in the presence of moisture and demonstrate water-dispersible fiber and the fibre of TENSILE STRENGTH, absorbability, pliability and fabric integrity.Fiber of the present invention and fibre do not need to there is oil, wax or aliphatic acid finishing agent, do not need to use the pigment of a large amount of (usual 10wt% or greater amount) or filler lump in processing procedure to prevent fiber or fuse yet.In addition, the fibre prepared by tencel of the present invention does not need adhesive, and is easily dispersed or dissolved in house or public sewerage.

In general embodiment, the invention provides water-dispersible fiber, it comprises the sulfonic polyester of the glass transition temperature (Tg) with at least 25 DEG C, and wherein said sulfonic polyester comprises:

(A) residue of one or more dicarboxylic acids;

(B) with the total amount of repetitive, the residue of at least one sulfomonomer of about 4 to about 40 % by mole, described sulfomonomer has 2 functional groups and one or more sulfonate groups be connected on aromatics or alicyclic ring, and wherein said functional group is hydroxyl, carboxyl or their combination;

(C) one or more diol residue, wherein with the total amount of diol residue, at least 25 % by mole is the polyethylene glycol with following structure:

Wherein n is the integer in 2 to about 500 scopes; With

(D) with the total amount of repetitive, the residue with the branched monomer of 3 or more functional groups of 0 to about 25 % by mole, wherein said functional group is hydroxyl, carboxyl or their combination.

Fiber of the present invention optionally can comprise the aqueous dispersion polymers blended with described sulfonic polyester, and optionally can comprise the nonaqueous dispersion polymer blended with described sulfonic polyester, and condition is described blend is immiscible blend.With the total weight of fiber, fiber of the present invention comprises the pigment or filler that are less than 10wt%.The present invention also comprises the fibre comprising these fibers, and can comprise personal care product, such as, wipe paper, gauze, chiffon, diaper, adult incontinent briefs, training pant, female sanitary towel, bandage and operation dressing.Described fibre can have one or more fibrous absorbent layer.

Fiber of the present invention can be homofil, bi-component or multicomponent fibre.Such as, fiber of the present invention by single sulfonic polyester or sulfonic polyester blend melt spinning being prepared, and can comprise staple fibre, monfil and the multifilament fiber with shaping cross section.In addition, the invention provides multicomponent fibre, such as U.S. Patent number 5,916, described in 678, it can by extruding preparation by sulfonic polyester and one or more and this sulfonic polyester immiscible nonaqueous dispersion polymer respectively by the spinning head with the horizontal geometry (such as " fabric of island-in-sea type ", core-skin type, parallel type or segmented pie configurations) be shaped or through designing.Thereafter by dissolving boundary layer or segmented pie and leaving the less long filament of one or more nonaqueous dispersion polymer described or fine-denier fiber and remove described sulfonic polyester.The fiber of these nonaqueous dispersion polymer has the fiber size more much smaller than the multicomponent fibre removed before sulfonic polyester.Such as, sulfonic polyester and nonaqueous dispersion polymer can be supplied to polymer distribution system, polymer be introduced the spinnerets of segmentation wherein.Polymer arrives fiber spinning jet along the path separated and merges at spinneret orifice place, and described spinneret orifice comprises two concentric circle holes provides sheath core fiber thus; Or comprise diametrically be divided into multiple part circular spinneret orifice to provide the fiber of parallel type.Selectively, immiscible water dispersible sulfonic polyester and nonaqueous dispersion polymer separately can be introduced the spinning head with multiple radial passage has segmented pie cross section multicomponent fibre with preparation.Typically, sulfonic polyester will form " skin " part of core-skin type structure.In the fiber cross section with multiple fragment, usual nonaqueous dispersion fragment is fully kept apart each other by sulfonic polyester.Selectively, can by following formation multicomponent fibre: the melting in the extruder separated by sulfonic polyester and nonaqueous dispersion polymer, and polymer flow is imported in a spinning head, described spinning head has point dispensing line of multiple little tubule or pieces, to provide the fiber with fabric of island-in-sea type shaping cross section.The example of this spinning head is described in U.S. Patent number 5,366, in 804.Usually, in the present invention, sulfonic polyester will form " sea " component, but not aqueous dispersion polymers will form " island " component.

Unless otherwise noted, all numerical value of the expression component content used in the specification and claims, character (such as molecular weight), reaction condition etc. all should be understood to all be modified by term " about " in all scenario.Therefore, unless the contrary indication, description is hereafter all approximation with the numerical parameter that provides in appended claim, and it can depend on the required character that the present invention will reach and change.In any case each numerical parameter all should at least according to reported number of significant figures and by applying the common technology of rounding off to explain.In addition, the scope provided in this description and claim is intended to clearly comprise gamut, and not only comprises end points.Such as, point out as the scope of 0-10 is intended to comprise: all integers between 0-10 (such as 1,2,3,4 etc.); All marks between 0-10 (such as 1.5,2.3,4.57,6.1113 etc.) and end points 0 and 10.Such as, and the scope relevant with chemical substituents, " C1-C5 hydrocarbon ", be intended to clearly comprise and disclose C1 and C5 hydrocarbon and C2, C3 and C4 hydrocarbon.

Although the number range and the parameter that provide wide region of the present invention are all approximations, the numerical value provided in a particular embodiment is as far as possible accurately reported.But any numerical value itself all comprises certain error, this error must be caused by the standard deviation existed in their respective test measurements.

Homofil of the present invention and the fibre prepared by homofil are water dispersibles, and at room temperature usually disperse completely.Higher water temperature can be used to accelerate, and it is dispersed and from the removal speed non-woven material or multicomponent fibre.The term " water dispersible " used for homofil and the fibre prepared by homofil is herein intended to have identical implication with term " water dissipation ", " water dispersible ", " water-soluble ", " clearing up property of water ", " water-soluble ", " water removal ", " water-soluble " and " water dispersible ", and is intended to expression fiber or fibre wherein or by it is dispersed or dissolved by acting on of water.Term " dispersion ", " dispersible ", " dissipation " or " can dissipate " represent the loose suspended substance or the slurry that use enough deionized waters (water of such as 100:1: fibre weight ratio) to form fiber or fibre; at the temperature of about 60 DEG C and in the time being no more than 5 days, this fiber or fibre dissolve, decompose or be separated into multiple loose sheet or particle; described or particle are more or less distributed in whole medium; make, by such as filtering or evaporating except anhydrating, discernible long filament to be reclaimed from this medium.Therefore, " water dispersible " used herein be not intended to comprise tangle or bonding but the simple decomposition of the fiber combinations part of water insoluble or nonaqueous dispersion, wherein said fiber combinations part splits off simply and produces the slurry of fiber in water in water, and this slurry can by receiving except anhydrating back and forth.In content of the present invention, all these terms all represent that the mixture of water or water and the cosolvent miscible with water is to the activity of sulfonic polyester described herein.The example of this cosolvent miscible with water comprises alcohol, ketone, glycol ethers, ester etc.Described term be intended to comprise wherein sulfonic polyester dissolve the situation that forms true solution and wherein sulfonic polyester be dispersed in the situation in water-bearing media.Usually, due to the statistics character of sulfonic polyester composition, soluble fraction and dispersion part may be had when single sulfonic polyester sample is put into water-bearing media.

Similarly, the term " water dispersible " used for the sulfonic polyester of a kind of component as multicomponent fibre or fibre herein is also intended to have identical implication with term " water dissipation ", " water dispersible ", " water-soluble ", " clearing up property of water ", " water-soluble ", " water removal ", " water-soluble " and " water dispersible ", and be intended to represent the effect of sulfonic polyester component by water from multicomponent fibre abundant remove and disperse or dissolve make it possible to discharge and be separated the nonaqueous dispersion fiber wherein comprised.Term " dispersion ", " dispersible ", " dissipation " or " can dissipate " represent the loose suspended substance or the slurry that use enough deionized waters (water of such as 100:1: fibre weight ratio) to form fiber or fibre, dissolve from multicomponent fibre with sulfonic polyester component in the time being no more than 5 days, decompose or be separated at about 60 DEG C of temperature, leave the multiple fine-denier fibers formed by nonaqueous dispersion fragment.

When the shaping cross section for describing multicomponent fibre, term " fragment (block) " or " territory " or " district " represent the region comprising nonaqueous dispersion polymer in described cross section, and the water dispersible sulfonic polyester that wherein these territories or fragment are namely between fragment or territory is fully kept apart each other.Term used herein " fully keep apart " be intended to represent fragment or territory separated from one another to allow sulfonic polyester to be removed time described fragment or territory form independently fiber.Fragment Huo Yuhuo district can have similar size and dimension or different size and dimensions.Equally, fragment Huo Yuhuo district can arbitrary configuration arrangement.These fragment Huo Yuhuo districts are " abundant continuous print " along the length of multicomponent extrudate or fiber.Described term " abundant continuous print " represents that at least 10cm length along multicomponent fibre is continuous print.When water dispersible sulfonic polyester is removed, fragment, the Yu Huo district of these multicomponent fibres produce nonaqueous dispersion polymer microfibers.

As pointed out in this description, the shaping cross section of multicomponent fibre can be the forms such as such as core-skin type, fabric of island-in-sea type, segmented pie, hollow fan-shaped block, eccentric segment block.

Water-dispersible fiber of the present invention is prepared by the polyester comprising dibasic carboxylic acid monomers's residue, sulfomonomer residue, diol monomer residue and repetitive (or more specifically sulfonic polyester).This sulfomonomer can be dicarboxylic acids, glycol or hydroxycarboxylic acid.Therefore term used herein " monomer residue " represents the residue of dicarboxylic acids, glycol or hydroxycarboxylic acid." repetitive " used herein represents the organic structure with the monomer residue that 2 are connected by carbonyl oxygen base.Sulfonic polyester of the present invention comprises sour residue (100 % by mole) and the diol residue (100 % by mole) of equimolar ratio substantially, and they make the total mole number of repetitive equal 100 % by mole with the reaction of equal proportion substantially.Therefore, the molar percentage provided in the present invention can be the total mole number in the total mole number of the total mole number of sour residue, diol residue or repetitive.Such as, sulfonic polyester comprises with the sulfomonomer of the total amount 30 % by mole of repetitive (it can be dicarboxylic acids, glycol or hydroxycarboxylic acid), represents that this sulfonic polyester comprises the sulfomonomer of 30 % by mole that account for 100 % by mole of repetitives altogether.Therefore, in the repetitive of every 100 moles, there are 30 moles of sulfomonomer residues.Similarly, sulfonic polyester comprises and represents that this sulfonic polyester comprises the sulfomonomer of 30 % by mole that account for 100 % by mole of sour residues altogether with the dicarboxylic acids sulfomonomer of the total amount 30 % by mole of sour residue.Therefore, in a kind of situation after this, in every 100 equimolar acid residues, there are 30 moles of sulfomonomer residues.

Sulfonic polyester as herein described has at least about 0.1dL/g, preferably about 0.2-0.3dL/g, most preferably be greater than the inherent viscosity (being hereinafter abbreviated as " Ih.V. ") of about 0.3dL/g, it records with the concentration of about 0.5g sulfonic polyester/100mL solvent in 25 DEG C of 60/40 parts by weight solution in phenol/tetrachloroethane solvent.Term used herein " polyester " comprises " equal polyester " and " copolyesters ", and represents the synthetic polymer prepared by the polycondensation of bifunctional carboxylic acid and difunctional hydroxyl compound.Term used herein " sulfonic polyester " represents any polyester comprising sulfomonomer.Usual bifunctional carboxylic acid is dicarboxylic acids, and difunctional hydroxyl compound is dihydroxylic alcohols, such as two hydroxyl alcohol and glycol.Selectively, bifunctional carboxylic acid can be hydroxycarboxylic acid, such as P-hydroxybenzoic acid, and difunctional hydroxyl compound can be the aromatic rings with 2 hydroxyl substituents, such as quinhydrones.Term used herein " residue " represents any organic structure by adopting in the polycondensation reaction of corresponding monomer introducing polymer.Therefore, di-carboxylic acid residue can come from dibasic carboxylic acid monomers or its relevant carboxylic acid halides, ester, salt, acid anhydrides or their mixture.Therefore, term dicarboxylic acids used herein is intended to any derivative comprising dicarboxylic acids and dicarboxylic acids, comprise carboxylic acid halides, ester, half ester, salt, half salt, acid anhydrides, mixed acid anhydride or their mixture that it is relevant, it can be used in the polycondensation process with glycol in order to prepare high molecular weight polyesters.

Sulfonic polyester of the present invention comprises one or more di-carboxylic acid residue.Depend on type and the concentration of sulfomonomer, di-carboxylic acid residue can account for about 60 to about 100 % by mole of sour residue.Other examples of the concentration range of di-carboxylic acid residue are about 60 % by mole to about 95 % by mole, about 70 % by mole to about 95 % by mole.The example of operable dicarboxylic acids to comprise in aliphatic dicarboxylic acid, Cycloaliphatic dicarboxylic acids, aromatic dicarboxylate or these acid two or more mixture.Therefore; the dicarboxylic acids be applicable to includes but not limited to: succinic acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid, fumaric acid, maleic acid, itaconic acid, 1; 3-cyclohexyl dicarboxylic acid, 1; 4-cyclohexyl dicarboxylic acid, diglycolic acid, 2; 5-norbornane dioctyl phthalate, phthalic acid, terephthalic acid (TPA), Isosorbide-5-Nitrae-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acids, diphenic acid, 4; 4 '-oxydibenzoic acid, 4,4 '-sulfonyl dibenzoic acid and M-phthalic acid.Preferred di-carboxylic acid residue is M-phthalic acid, terephthalic acid (TPA) and 1, the residue of 4-cyclohexyl dicarboxylic acid, if or employ diester, then dimethyl terephthalate (DMT), dimethyl isophthalate and 1, the residue of 4-cyclohexyl dicarboxylic acid dimethyl ester, the especially preferably residue of M-phthalic acid and terephthalic acid (TPA).Although dicarboxylic acids methyl esters is the most preferred embodiment, comprising more senior Arrcostab (such as ethyl ester, propyl diester, isopropyl esters, butyl ester etc.) is also acceptable.In addition, aromatic ester can also be used, particularly phenylester.

With the total amount of repetitive, sulfonic polyester comprises the residue of at least one sulfomonomer of about 4 to about 40 % by mole, described sulfomonomer has 2 functional groups and one or more sulfonate groups be connected on aromatics or cyclic aliphatic ring, and wherein said functional group is hydroxyl, carboxyl or their combination.With the total amount of repetitive, other examples of the concentration range of sulfomonomer residue are about 4 to about 35 % by mole, about 8 to about 30 % by mole and about 8 to about 25 % by mole.Sulfomonomer can be comprise sulfonate groups dicarboxylic acids or its ester, comprise the glycol of sulfonate groups or comprise the carboxylic acid of sulfonate groups.Term " sulfonate " represents to have "-SO ₃m " sulfonate of structure, wherein M is the CATION of this sulfonate.But the CATION metal ion of this sulfonate, such as Li ⁺, Na ⁺, K ⁺, Mg ⁺⁺, Ca ⁺⁺, Ni ⁺⁺, Fe ⁺⁺deng.Selectively, the CATION of this sulfonate can be nonmetallic, such as nitrogenous base, as such as U.S. Patent number 4,304, described in 901.Based on the CATION of nitrogen derived from nitrogenous alkali, it can be the compound of aliphatic, cyclic aliphatic or aromatics.The example of this nitrogenous base comprises ammonia, dimethylethanolamine, diethanol amine, triethanolamine, pyridine, morpholine and piperidines.Because comprise based on the sulfonate of nitrogen monomer make under the condition needed for polymer melting normally heat-labile, therefore the present invention for the preparation of the method for the sulfonic polyester of the sulfonate groups comprised based on nitrogen be the sulfonate groups of alkali metal salt by comprising aequum polymer dispersed, dissipate or be dissolved in water then with the cation exchange alkali metal cation based on nitrogen.

When the CATION using monoacidic base metal ion as sulfonate, the sulfonic polyester obtained can be dispersed in water completely, and dispersion rate depends on the temperature of sulfomonomer content in the polymer, water, the surface area/thickness etc. of sulfonic polyester.When using bivalent metal ion, the sulfonic polyester obtained is not easy disperseed by cold water and more easily disperseed by hot water.Can use more than a kind of counter ion in single polymers composition, and the means of the water-responsive of modulation or fine setting resulting product can be provided like this.The example of sulfomonomer residue comprises the monomer residue that wherein sulfonate groups is connected to aromatic acid ring (such as benzene, naphthalene, biphenyl, diphenyl ether, sulfonyl hexichol and diphenyl-methane) or cyclic aliphatic ring (such as cyclohexyl, cyclopentyl, cyclobutyl, suberyl and ring octyl group).Other examples that can be used for the sulfomonomer residue in the present invention are sulfosalicylic phthalate, sulfoterephthalic, the metal sulfonate of sulfoisophthalic acid or their combination.Other examples of operable sulfomonomer are that 5-sodium is for sulfoisophthalic acid and ester thereof.If sulfomonomer residue is from 5-sodium for sulfoisophthalic acid, so in the total mole number of sour residue, typical sulfomonomer concentration range is about 4 to about 35 % by mole, about 8 to about 30 % by mole and about 8 to about 25 % by mole.

In sulfonic polyester preparation, sulfomonomer used is known compound and method as known in the art can be used to prepare.Such as, wherein then the sulfomonomer that is connected to aromatic rings of sulfonate groups can react obtained sulfonate and prepare by obtaining corresponding sulfonic acid with fuming sulphuric acid sulfonated aromatic compound with metal oxide or alkali (such as sodium acetate).The preparation section of various sulfomonomer is described in such as U.S. Patent number 3,779,993,3,018,272 and 3,528, in 947.

Also such as sulfonate sodium can be used to prepare polyester, and when described polymer is in discrete form, use ion-exchange process other ions (such as zinc) to replace sodium.Such ion-exchange process is usually better than preparing polymer with divalent salts, because sodium salt more dissolves in polymer reaction thing melting behaviors usually.

Sulfonic polyester comprises one or more diol residue, and it can comprise aliphatic, cyclic aliphatic and aralkyl glycol.Cycloaliphatic diol (such as 1,3-and Isosorbide-5-Nitrae-cyclohexanedimethanol) can exist as the mixture of their pure cis or transisomer or cis and transisomer.Term used herein " glycol " is the synonym of term " two hydroxyl alcohol ", all represents any dihydroxylic alcohols.The example of glycol includes but not limited to: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1, ammediol, 2, 4-dimethyl-2-ethyl 1, 3-hexylene glycol, 2, 2-dimethyl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, 2-ethyl-2-isobutyl group-1, ammediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexylene glycol, 2, 2, 4-trimethyl-1, 6-hexylene glycol, thiodiethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol, one or more combination in terephthalyl alcohol or these glycol.

With the total amount of diol residue, diol residue can comprise the residue with the polyethylene glycol of following structure of about 25 % by mole to about 100 % by mole:

Wherein n is the integer in 2 to about 500 scopes.The limiting examples of the polyethylene glycol (such as wherein n is 2-6) of lower molecular weight is: diethylene glycol, triethylene glycol and TEG.In the glycol of these lower molecular weights, most preferably diethylene glycol and triethylene glycol.Wherein n is that the polyethylene glycol (being abbreviated as herein " PEG ") of the higher molecular weight of 7 to about 500 comprises the known product commercially available with title CARBOWAX, and it is the Union Carbide before Dow Chemical Company() product.Usually, PEG is combined with other glycol (such as diethylene glycol or ethylene glycol).Based on the value (it is in the scope being greater than 6 to 500) of n, molecular weight can in the scope being greater than 300 to about 22,000g/mol.Molecular weight and % by mole each other in inverse ratio, especially, along with molecular weight improves, % by mole will to reduce with the hydrophily reaching given extent.Such as, the example of this design is 10 % by mole at the most that PEG that supposition has a molecular weight of 1000 can account for glycol total amount, and has 10, and the PEG of the molecular weight of 000 introduces with the level of 1 % by mole being less than glycol total amount usually.

Due to some dimerization of side reaction possibility in-situ preparation, trimerization and four polyglycols, described side reaction can be controlled by changing process conditions.Such as, when polycondensation reaction is carried out in acid condition, ethylene glycol may generate different diethylene glycol, triethylene glycol and the TEG measured by incidental acid catalyst dehydration.Can add in reactant mixture and well known to a person skilled in the art that cushioning liquid is to delay these side reactions.But if save cushioning liquid and allow to occur dimerization, trimerization and four poly-reactions, then other compositing ranges are also possible.

With the total amount of repetitive, sulfonic polyester of the present invention can comprise the residue that 0 to about 25 % by mole has the branched monomer of 3 or more functional groups, and wherein said functional group is hydroxyl, carboxyl or their combination.The limiting examples of branched monomer is 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, glycerol, pentaerythrite, erythroglucin, threitol, dipentaerythritol, D-sorbite, triphen six acid anhydride, pyromellitic acid dianhydride, dihydromethyl propionic acid or their combination.Other examples of branching monomer concentration scope are 0 to about 20 % by mole and 0 to about 10 % by mole.The existence of branched monomer may bring many possible benefits for sulfonic polyester of the present invention, includes but not limited to: the ability regulating rheological characteristic, dissolubility and tensile property.Such as, when molecular weight is constant, branched sulphonic polyester also will have larger ends concentration compared with linear analogues, and this may be conducive to the cross-linking reaction after being polymerized.But, when branching agent concentration is higher, confirm that sulfonic polyester may gelation.

Fiber of the present invention sulfonic polyester used has the glass transition temperature (being abbreviated as " Tg ") of at least 25 DEG C herein, and its use well known to a person skilled in the art that standard technique (such as Differential Scanning Calorimetry (" DSC ")) records dry polymeric.It is use " dry polymeric " (namely by polymer being heated to the temperature of about 200 DEG C and make sample return polymer samples that room temperature therefrom drives away water that is external or that absorb) to carry out that the Tg of sulfonic polyester of the present invention measures.Usually, dry sulfonic polyester in DSC instrument by the following method: carry out the first heat scan, wherein sample is heated to above the temperature of water evaporating temperature; Sample is remained on described temperature, until the water absorbed in polymer evaporates (showing as large wide endothermic peak) completely; By sample cool to room temperature; Then the second heat scan is carried out to obtain Tg measured value.Other examples of the glass transition temperature that sulfonic polyester demonstrates are at least 30 DEG C, at least 35 DEG C, at least 40 DEG C, at least 50 DEG C, at least 60 DEG C, at least 65 DEG C, at least 80 DEG C and at least 90 DEG C.Although other Tg are also possible, the typical glass state transition temperature of dry sulfonic polyester of the present invention is about 30 DEG C, about 48 DEG C, about 55 DEG C, about 65 DEG C, about 70 DEG C, about 75 DEG C, about 85 DEG C and about 90 DEG C.

Tencel of the present invention can be made up of above-mentioned sulfonic polyester or substantially be made up of it.But in another embodiment, sulfonic polyester of the present invention can be single polyester or can with one or more supplementary polyblends to change the character of gained fiber.Depend on application, described supplementary polymer can yes or no water dispersible and can with described sulfonic polyester miscible or unmixing.If this supplementary polymer is nonaqueous dispersion, blend that is so preferred and sulfonic polyester is immiscible.Term used herein " (can) be miscible " is intended to represent that described blend has single homogeneous amorphous phase, shows as the Tg that single composition relies on.Such as, can use and the first polymer of the second Polymers Miscibility next " plasticising " second polymer, as such as U.S. Patent number 6,211, illustrative in 309.Relatively, term used herein " (can) be not miscible " represents that blend demonstrates the phase of at least two random mixing and demonstrates more than one Tg.Some polymer may with sulfonic polyester unmixing but still be compatible.The generality of the various analytical technologies of miscible and immiscible blend polymer and feature thereof describes and is found in Polymer Blends the 1st and the 2nd volume, D.R. Paul and C.B. Bucknall writes, 2000, John Wiley & Sons, Inc..

The limiting examples of aqueous dispersion polymers that can be blended with sulfonic polyester is: polymethylacrylic acid, PVP, polyethylene-propylene acid copolymer, polyvinyl methyl ether, polyvinyl alcohol, polyethylene glycol oxide, hydroxy propyl cellulose, hydroxypropyl methylcellulose, methylcellulose, ethylhydroxyethylcellulose, isopropyl cellulose, methyl ether starch, polyacrylamide, poly-(N-caprolactam), PEOz, poly-(2-isopropyl-2-oxazoline), Ju vinyl methyl oxazolidinone, water dispersible sulfonic polyester, poly-ethene ylmethyl oxazolidinedione, poly-(2, 4-dimethyl-6-triazine radical ethene) and ethylene oxide-propylene oxide copolymer.The example of nonaqueous dispersion polymer that can be blended with sulfonic polyester includes but not limited to: polyolefin (such as polyethylene and polyacrylic homopolymers and copolymer), polyethylene terephthalate, polybutylene terephthalate (PBT) and polyamide (such as nylon-6), polyactide, caprolactone, Eastar Bio (poly-(tetramethylene adipate ester-copolymerization-terephthalate), the product of Eastman Chemical Company), Merlon, polyurethane and polyvinyl chloride.

According to the present invention, the blend more than a kind of sulfonic polyester can be used to modulate the final utilization character of obtained fiber or fibre (such as bondedfibre fabric or nonwoven web).The blend of one or more sulfonic polyesters will have the Tg of at least 25 DEG C (for water dispersible one-component fibers) and at least 57 DEG C (for multicomponent fibres).Therefore, blended also may be used for changes the machining feature of sulfonic polyester so that prepare nonwoven articles.In another embodiment, the unmixing blend of polypropylene and sulfonic polyester can provide conventional nonwoven web, and it can split off and be dispersed in water completely in water, because do not need really to dissolve.After this in a kind of example, required performance relate to keep polyacrylic physical property simultaneously sulfonic polyester in the actual use procedure of product be only onlooker or selectively sulfonic polyester be fugitive, be just removed before the final form using product.

Sulfonic polyester and supplementary polymer can be blended in batch (-type), semi continuous or continuous process.Before melt spinning becomes fiber, easily can well known to a person skilled in the art small-scale batch of preparation in any high strength mixing arrangement (such as Banbury mixer).Described component also can be blended in the solution being arranged in appropriate solvent.Melt-mixing method comprise by sulfonic polyester and supplementary polymer be enough at the temperature melting described polymer blended.Described blend can be cooled and granulate with for subsequent use, or described melt blended material directly can be become fibers form by this melt blended material melt spinning.Term used herein " fusing (melting) " includes but not limited to only make described polyester soften.For melting mixing method known in polymer arts, see Mixing and Compounding of Polymers, (I. Manas-Zloczower & Z. Tadmor writes, Carl Hanser Verlag Publisher, 1994, New York, N. Y.).

Present invention also offers water-dispersible fiber, it comprises the sulfonic polyester of the glass transition temperature (Tg) with at least 25 DEG C, and wherein said sulfonic polyester comprises:

(A) with the total amount of sour residue, one or more M-phthalic acids of about 50 to about 96 % by mole or the residue of terephthalic acid (TPA);

(B) with the total amount of sour residue, the sodium of about 4 to about 30 % by mole is for the residue of sulfoisophthalic acid;

Wherein n is the integer in 2 to about 500 scopes;

(D) with the total amount of repetitive, the residue with the branched monomer of 3 or more functional groups of 0 to about 20 % by mole, wherein said functional group is hydroxyl, carboxyl or their combination.

As mentioned above, described fiber optionally can comprise first aqueous dispersion polymers blended with described sulfonic polyester and the optional nonaqueous dispersion polymer blended with described sulfonic polyester makes described blend be immiscible blend.With the total weight of fiber, described fiber comprises the pigment or filler that are less than 10wt%.First aqueous dispersion polymers is described above.Sulfonic polyester should have the glass transition temperature (Tg) of at least 25 DEG C, but also can have the Tg of such as about 35 DEG C, about 48 DEG C, about 55 DEG C, about 65 DEG C, about 70 DEG C, about 75 DEG C, about 85 DEG C and about 90 DEG C.Described sulfonic polyester can comprise the isophthalic acid residues of other concentration, such as about 60 to about 95 % by mole and about 75 to about 95 % by mole.More examples of isophthalic acid residues concentration range are about 70 to about 85 % by mole, about 85 to about 95 % by mole and about 90 to about 95 % by mole.Sulfonic polyester can also comprise the diethylene glycol residue of about 25 to about 95 % by mole.Other examples of diethylene glycol residue concentration range comprise about 50 to about 95 % by mole, about 70 to about 95 % by mole and about 75 to about 95 % by mole.Sulfonic polyester can also comprise the residue of ethylene glycol and/or Isosorbide-5-Nitrae-cyclohexanedimethanol (being abbreviated as " CHDM ") herein.The typical concentration range of CHDM residue is about 10 to about 75 % by mole, about 25 to about 65 % by mole and about 40 to about 60 % by mole.The typical concentration range of glycol residue is about 10 to about 75 % by mole, about 25 to about 65 % by mole and about 40 to about 60 % by mole.In another embodiment, described sulfonic polyester comprises the isophthalic acid residues of about 75 to about 96 % by mole and the diethylene glycol residue of about 25 to about 95 % by mole.

Sulfonic polyester of the present invention easily uses typical polycondensation reaction condition to prepare by the dicarboxylic acids be applicable to, ester, acid anhydrides or salt, sulfomonomer and applicable glycol or diol mixture.They by continuous, semicontinuous or andnon-continuous operation manner preparation, and can use various type of reactor.The example of the type of reactor be applicable to includes but not limited to: agitator tank, continuous agitator tank, slurry reactor, tubular reactor, scraped film type reactor, falling film reactor or extrusion reaction device.Term used herein " continuously " represents the technique wherein introduced reactant in an uninterrupted manner simultaneously and take out product." continuously " represents that described technique is operationally substantially or totally continuous and for relative with " intermittently " technique." continuously " never means forbid normal interruption in process continuity, such as owing to starting, reactor servicing or predetermined dwelling period.Term used herein " intermittently " technique represents the technique wherein being added by all reactants and then carry out processing (no longer supply material for reactor during this period or take out material from reactor) in reactor according to default course of reaction.Term " semicontinuous " represents and wherein adds some reactants when technique starts and supply the technique of remaining reaction thing continuously along with reaction.Selectively, half-continuous process also can comprise the process similar with batch process, and wherein all reactants all add when technique starts, just along with reaction carries out one or more products to remove continuously.For economic reasons and in order to prepare the good polymer of dyeing, described process advan ground is as continuous processing operation, because if make it be detained the long time in the reactor at elevated temperatures, the outward appearance of described sulfonic polyester may be deteriorated.

Sulfonic polyester of the present invention is prepared by operation well known by persons skilled in the art.Sulfomonomer is directly added in the reactant mixture for the preparation of polymer usually, but known and also can use other techniques, such as U.S. Patent number 3,018,272,3,075,952 and 3,033, described in 822.Normal polyester polymerizing condition can be used to carry out the reaction of sulfomonomer, diol component and dicarboxylic acid component.Such as, when preparing sulfonic polyester by ester exchange reaction (namely by the ester-formin of dicarboxylic acid component), course of reaction can comprise two steps.In a first step, diol component and dicarboxylic acid component's (such as dimethyl isophthalate) react about 0.5 to about 8 hour in the temperature (typically about 150 DEG C to about 250 DEG C) raised and about 0.0kPa gauge pressure to the pressure of about 414kPa gauge pressure (60 pounds/square inch, " psig ").Preferably, the temperature of ester exchange reaction is within the scope of about 180 DEG C to about 230 DEG C, and the reaction time is about 1 to about 4 hour, and preferred pressure is in 103kPa gauge pressure (15psig) to about 276kPa gauge pressure (40psig) scope.Then, by product at higher temperature and heated under reduced pressure to generate sulfonic polyester, remove glycol, it is easily volatilization removing from system under these conditions simultaneously.Second step (or condensation polymerization step) continues in higher vacuum with usually at about 230 DEG C to about 350 DEG C, preferably about 250 DEG C to about 310 DEG C and most preferably from about continue about 0.1 to about 6 hour at the temperature of 260 DEG C to about 290 DEG C, or preferably about 0.2 to about 2 hour, until obtain the polymer with the required degree of polymerization, the degree of polymerization is by characteristic viscosity determining.Condensation polymerization step can be held in the palm at about 53kPa(400) hold in the palm to about 0.013kPa(0.1) carry out under decompression in scope.All use the condition stirred or be applicable to guarantee abundant heat transfer and the Surface Renewal of reactant mixture two stages.The reaction in two stages is all promoted by the catalyst be applicable to, and this catalyst is alkoxy titanium compound, alkali metal hydroxide and alkoxide, organic carboxylate, Alkyzin compound, metal oxide etc. such as.Also can use and U.S. Patent number 5,290, the three sections of similar preparation sections described in 631, particularly when using the mix monomer raw material of acid and ester.

For guaranteeing to impel diol component and dicarboxylic acid component by ester exchange reaction mechanism complete reaction, preferably use about 1.05 to about 2.5 mole percent diol component/1 moles of dicarboxylic acids present components.But, it will be understood by those skilled in the art that what the ratio of diol component and dicarboxylic acid component was normally determined by the design of the reactor that described course of reaction occurs wherein.

Preparing in sulfonic polyester by direct esterification (namely by the sour form of dicarboxylic acid component), sulfonic polyester reacts to prepare by making dicarboxylic acids or dicarboxylic acids mixture and diol component or diol component mixture.Described reaction be about 7kPa gauge pressure (1psig) to about 1379kPa gauge pressure (200psig), preferably lower than 689kPa(100psig) pressure under carry out, to prepare the sulfopolyester product of low-molecular-weight linear or branching, it has the average degree of polymerization of about 1.4 to about 10.The temperature used in direct esterification course of reaction usually within the scope of about 180 DEG C to about 280 DEG C, more preferably within the scope of about 220 DEG C to about 270 DEG C.Then described low-molecular weight polymer can pass through polycondensation polymerized.

Water dispersible multicomponent fibre of the present invention and fibre can also comprise other can not cause adverse effect conventional additives and composition to its final use.Such as, such as following additive can be used: filler, surface friction modifiers, light and thermally stable agent, extrusion aid, antistatic additive, colouring agent, dyestuff, pigment, fluorescent whitening agent, antiseptic, anti-fake mark, hydrophobic and hydrophilic enhancers, viscosity improver, slipping agent, flexibilizer, adhesion promoter etc.

Fiber of the present invention and fibre are not sought survival and are prevented fiber from luming in process or fusing at additive (such as pigment, filler, oil, wax or aliphatic acid finishing agent).Term used herein " caking or fusion " is interpreted as that representing that fiber or fibre stick together or fuse into block makes fiber can not be processed or otherwise utilized to the object of its expection.In the process of fiber or fibre or store caking and fusion can occur during time-of-week for several days or a few, and can worsen under wet heat condition.

In one embodiment of the present invention, with the total weight of fiber or fibre, fiber and fibre comprise this kind of anti-caking additive being less than 10wt%.Such as, fiber and fibre can comprise the pigment or filler that are less than 10wt%.In another example, with the total weight of fiber, fiber and fibre can comprise and be less than 9wt%, are less than 5wt%, are less than 3wt%, are less than the pigment of 1wt% and 0wt% or filler.Colouring agent (sometimes also referred to as toner) can be added and give neutralc tint needed for sulfonic polyester and/or whiteness.When needing color fibre, pigment or colouring agent can be comprised in sulfonic polyester reactant mixture in the course of reaction of diol monomer and dibasic carboxylic acid monomers, or can by them and prefabricated sulfonic polyester melt blending.The method for optimizing introducing colouring agent is the colouring agent using heat-staple coloured organic compound with band reactive group, makes this colouring agent copolymerization and is attached in sulfonic polyester to improve its tone.Such as, colouring agent is as having the dyestuff of reactive hydroxyl and/or carboxyl, and include but not limited to blue and red substituted anthraquinone, it can be copolymerized in polymer chain.When using dyestuff as colouring agent, after ester exchange or direct esterification reaction, they can be added in copolyesters course of reaction.

For the purposes of the present invention, term " fiber " represents the condensate with high aspect ratio, and it can form two dimension or three-dimensional article (such as woven fabric or bondedfibre fabric).In the context of the present invention, term " fiber " and " fibers " synonym and be intended to represent one or more fiber.Fiber of the present invention can be homofil, bi-component or multicomponent fibre.Term used herein " homofil " is intended to represent the fiber by being prepared by the blend melt spinning of the blend of single sulfonic polyester, one or more sulfonic polyesters, one or more sulfonic polyesters and one or more other polymer, and it comprises staple fibre, monfil and multifilament fiber." one pack system " is intended to term " one-component " synonym and comprises " two composition " or " multicomponent " fiber, represents and extrudes by least two kinds of polymer the fiber formed as blend from same extruder.The cross-sectional area that one pack system or biconstitutent fibre do not traverse this fiber is arranged in the various polymers compositionss in the zones of different of position relative constancy, and various polymer is discontinuous along the whole length of fiber usually, but usually form starting point and the terminal all fibril of random or protofibrils.Therefore, term " one pack system " is not intended to get rid of the fiber formed by the blend of polymer or one or more polymer, can add a small amount of additive wherein for painted, anti-static function, lubricity, hydrophily etc.

Relatively, term used herein " multicomponent fibre " is intended to represent by by the melting obtained multistrand polymer conductance is entered and to have in the spinning head of multiple points of dispensing line but the common spinning fiber that forms a fiber and prepare in the extruder separated of two or more processbearing astrocyte polymer.Multicomponent fibre is sometimes also referred to as conjugate fiber or bicomponent fiber.Polymer traverses the cross sectional arrangement of conjugate fiber in the different fragments or region of position substantial constant, and extends continuously along the length of conjugate fiber.The configuration of this multicomponent fibre can be such as core-sheath configuration, wherein a kind of polymer by another kind of polymer around, or can be side by side configuration, fan-shaped (pie) configuration or " fabric of island-in-sea type " configuration.Such as, multicomponent fibre can be prepared by sulfonic polyester and one or more nonaqueous dispersion polymer being extruded through respectively the spinning head with the horizontal geometry (such as " fabric of island-in-sea type " or segmented pie configurations) be shaped or through designing.Multicomponent fibre normally has the staple fibre of definite shape or circular cross section, monofilament or multifilament fiber.Most of fibers form is heat cure.Described fiber can comprise various antioxidant as described herein, pigment and additive.

The size of monfil is usually in about 15 to about 8000 dawn/long filament (being abbreviated as herein " d/f ") scope.Tencel of the present invention has the d/f value in about 40 to about 5000 scopes usually.Monofilament can be the form of one pack system or multicomponent fibre.Multifilament fiber of the present invention is preferably dimensioned to be from about 1.5 microns (meltblown fiber web), about 0.5 to about 50d/f(staple fibre) until about 5000d/f(monfil).Multifilament fiber also can be used as curling or not curling yarn and tow.Fiber used in meltblown fiber web and melt spinning fabric can the preparation of micro Denier size.Term used herein " micro Denier " is intended to represent that d/f value is for 1d/f or less.Such as, fine-denier fiber of the present invention has the d/f value of 1 or less, 0.5 or less or 0.1 or less usually.Electrospun nanofibers can also be passed through.

As mentioned above, sulfonic polyester is for the preparation of having the bi-component of shaping cross section and multicomponent fibre is also favourable.We find to have the sulfonic polyester of the glass transition temperature (Tg) of at least 57 DEG C or sulfonic polyester blend is specially adapted to multicomponent fibre to prevent caking and the fusion of fiber in spinning and turn-up process.Therefore, the invention provides the multicomponent fibre with shaping cross section, it comprises:

(A) water dispersible sulfonic polyester, it has the glass transition temperature (Tg) of at least 57 DEG C, and described sulfonic polyester comprises:

The residue of (i) one or more dicarboxylic acids;

(ii) with the total amount of repetitive, the residue of at least one sulfomonomer of about 4 to about 40 % by mole, described sulfomonomer has 2 functional groups and one or more sulfonate groups be connected on aromatics or alicyclic ring, and wherein said functional group is hydroxyl, carboxyl or their combination;

Wherein n is the integer in 2 to about 500 scopes; With

(B) multiple fragment, described fragment comprises one or more and the immiscible nonaqueous dispersion polymer of described sulfonic polyester, and the described sulfonic polyester that wherein said fragment is namely between fragment is fully kept apart each other;

Wherein said fiber has fabric of island-in-sea type or segmented pie cross section, and with the total weight of fiber, comprises the pigment or filler that are less than 10wt%.

Dicarboxylic acids, glycol, sulfonic polyester, sulfomonomer and branching monomer residues are as above for as described in other embodiments of the present invention.For multicomponent fibre, the Tg that sulfonic polyester has at least 57 DEG C is favourable.Other examples of the glass transition temperature that the sulfonic polyester of multicomponent fibre of the present invention or sulfonic polyester blend can demonstrate are at least 60 DEG C, at least 65 DEG C, at least 70 DEG C, at least 75 DEG C, at least 80 DEG C, at least 85 DEG C and at least 90 DEG C.In addition, in order to obtain the sulfonic polyester with at least 57 DEG C of Tg, the blend of one or more sulfonic polyesters of different proportion can be used to obtain having the sulfonic polyester blend of required Tg.The Tg of sulfonic polyester blend can be calculated by the weight average of the Tg using sulfonic polyester component.Such as, have the Tg of 48 DEG C sulfonic polyester can to have the sulfonic polyester of the Tg of 65 DEG C blended with the sulfonic polyester blend of the Tg obtaining having about 61 DEG C with 25:75 wt:wt ratio with another kind.

In another embodiment of the present invention, the water dispersible sulfonic polyester component of described multicomponent fibre have can meet following in the character of at least one:

(A) can by described multicomponent fibre spinning to required low denier;

(B) sulfonic polyester in these multicomponent fibres tolerates and removes but can effectively remove at elevated temperatures after Hydroentangled in the fibroreticulate hydroentanglement procedure be made up of described fiber; With

(C) described multicomponent fibre thermal curable is to generate stable firmly fabric.

The sulfonic polyester with specific melt viscosity and sulfomonomer residue levels is used to achieve unexpected and unforeseeable result when promoting these objects.

Therefore, in embodiments of the invention, provide the multicomponent fibre with shaping cross section, it comprises:

(A) at least one water dispersible sulfonic polyester; With

(B) multiple territory, described territory comprises the not miscible nonaqueous dispersion polymer of one or more and described sulfonic polyester, and the sulfonic polyester that wherein said territory is namely between territory is fully kept apart each other,

Wherein measure with the strain rate of 1 rad/sec at 240 DEG C, described water dispersible sulfonic polyester demonstrates and is less than about 12, the melt viscosity of 000 pool; With

Wherein in the total mole number of diacid or diol residue, described sulfonic polyester comprises the residue of at least one sulfomonomer being less than about 25 % by mole.

The sulfonic polyester used in these multicomponent fibres has and is usually less than about 12, the melt viscosity of 000 pool.Preferably, measure with the shear rate of 1 rad/sec at 240 DEG C, the melt viscosity of described sulfonic polyester is less than 10,000 pool.Be more preferably less than 6,000, be most preferably less than 4,000 pool.On the other hand, measure with the shear rate of 1 rad/sec at 240 DEG C, described sulfonic polyester demonstrates the melt viscosity that about 1000-12000 moors, more preferably 2000-6000 pool, most preferably 2500-4000 pool.Before mensuration viscosity, described sample 60 DEG C in vacuum drying oven dry 2 days.Melt viscosity on rheometer, uses the parallel-plate shape of 25mm diameter to arrange with the gap of 1mm record.Dynamic frequency scanning runs with the strain amplitude of the strain rate of 1-400rad/sec and 10%.Then viscosity is measured in the strain rate of 240 DEG C and 1 rad/sec.

Usually be less than about 25 % by mole according to the sulfomonomer residue content in the sulfopolyester polymer that this uses on the one hand of the present invention, be preferably less than 20 % by mole, be more than reported to the percentage accounting for diacid or diol residue total amount in sulfonic polyester.More preferably, this content is about 4 to about 20 % by mole, even more preferably from about 5 to about 12 % by mole, most preferably from about 7 to about 10 % by mole.The sulfomonomer that the present invention uses preferably has 2 functional groups and one or more sulfonate groups be connected on aromatics or cyclic aliphatic ring, and wherein said functional group is hydroxyl, carboxyl or their combination.Particularly preferably sulph M-phthalic acid monomer.

Except aforementioned sulfomonomer, sulfonic polyester preferably comprises one or more di-carboxylic acid residue; One or more diol residue, wherein with the total amount of diol residue, at least 25 % by mole is the polyethylene glycol with following structure:

Wherein n is the integer in 2 to about 500 scopes; With with the total amount of repetitive, the residue with the branched monomer of 3 or more functional groups of 0 to about 20 % by mole, wherein said functional group is hydroxyl, carboxyl or their combination.

In particularly preferred embodiments, described sulfonic polyester comprises the diol residue (total % by mole is 200%, i.e. 100% diacid and 100 % by mole of glycol) of the di-carboxylic acid residue of about 80-96 % by mole, the sulfomonomer residue of about 4 to about 20 % by mole and 100 % by mole.More particularly, the dicarboxylic acids part of described sulfonic polyester comprises about 60-80 % by mole terephthalic acid (TPA), about 0-30 % by mole M-phthalic acid and about 4-20 % by mole of 5-sodium for sulfoisophthalic acid (5-SSIPA).Glycol moiety comprises about 0-50 % by mole diethylene glycol and about 50-100 % by mole ethylene glycol.Exemplary formulation according to this embodiment of the present invention will be provided subsequently.

?	Approx. molar %(is in the total mole number of glycol or diacid residues)
		Terephthalic acid (TPA)	71
M-phthalic acid	20
		5-SSIPA	9
Diethylene glycol	35
		Ethylene glycol	65

The nonaqueous dispersion component of described multicomponent fibre can comprise those nonaqueous dispersion polymer described herein arbitrarily.The spinning of described fiber also can be carried out according to any means described herein.But the rheological equationm of state according to the improvement of the multicomponent fibre of this one side of the present invention provides the draw speed of raising.By sulfonic polyester and nonaqueous dispersion polymer-extruded to prepare multicomponent extrudate time, any means disclosed herein can be used by multicomponent extrudate with at least about 2000m/min, more preferably at least about 3000m/min, even more preferably at least about 4000m/min, most preferably at least about the speed fusion drawn of 4500m/min to prepare multicomponent fibre.Be bound by theory although be not meant to, described multicomponent extrudate creates the degree of crystallinity of at least some orientation in nonaqueous dispersion component at described multicomponent fibre of the fusion drawn of these speed.The degree of crystallinity of this orientation can improve the DIMENSIONAL STABILITY of the non-woven material be made up of described multicomponent fibre in following process process.

Another advantage of described multicomponent extrudate is that it can fusion drawn become to have the multicomponent fibre being spun into denier being less than 6 dawn/long filament.Other scopes of multicomponent fibre size comprise be less than 4 dawn/long filament and be less than 2.5 dawn/long filament be spun into denier.

Therefore, in another embodiment of the present invention, be the multicomponent extrudate with shaping cross section, it comprises:

(A) at least one water dispersible sulfonic polyester; With

(B) multiple territory, described territory comprises the not miscible nonaqueous dispersion polymer of one or more and described sulfonic polyester, and the described sulfonic polyester that wherein said territory is namely between territory is fully kept apart each other,

Wherein said extrudate can with the speed fusion drawn at least about 2000m/min.

Described multicomponent fibre comprises multiple fragment or the territory of one or more and described sulfonic polyester immiscible nonaqueous dispersion polymer, and the described sulfonic polyester that wherein said fragment or territory are namely between fragment or territory is fully kept apart each other.Term used herein " is fully kept apart " and is intended to represent that described fragment or territory are separated from each other and makes described fragment or territory after the described sulfonic polyester of removing can form independently fiber.Such as, described fragment or territory can contact with each other as such as segmented pie configurations but can split off by collision or when removing described sulfonic polyester.

In multicomponent fibre of the present invention, the weight ratio of sulfonic polyester and nonaqueous dispersion polymers compositions is usually within the scope of about 60:40 to about 2:98, or in another example within the scope of about 50:50 to about 5:95.Usually, described sulfonic polyester accounts for the 50wt% or less of multicomponent fibre gross weight.

The fragment of multicomponent fibre or territory can comprise one or more nonaqueous dispersion polymer.The example that may be used for the nonaqueous dispersion polymer in the fragment of described multicomponent fibre includes but not limited to: polyolefin, polyester, polyamide, polyactide, polycaprolactone, Merlon, polyurethane, cellulose esters and polyvinyl chloride.Such as, nonaqueous dispersion polymer can be polyester, such as polyethylene terephthalate, polybutylene terephthalate (PBT), poly-cyclohexyl dicarboxylic acid hexamethylene diester, cyclohexanedimethanol's diester, polytrimethylene terephthalate etc.In another example, it be biodegradable and/or according to ASTM standard method that described nonaqueous dispersion polymer can measure according to DIN Standard 54900, and it is biodegradable that D6340-98 measures.The example of biodegradable polyester and polyester blend is disclosed in U.S. Patent number 5,599, and 858,5,580,911,5,446,079 and 5,559, in 171.The term " biodegradable " used for nonaqueous dispersion polymer of the present invention is herein interpreted as and represents that described polymer (such as in compost environment) under ambient influnence can be degraded in suitable verifiable time span, as such as name is called the ASTM standard method of " Standard Test Methods for Determining Aerobic Biodegradation of Radiolabeled Plastic Materials in an Aqueous of Compost Envionment ", defined in D6340-98.Nonaqueous dispersion polymer of the present invention can also be " biodegradable ", represents that described polymer is easily broken in compost environment, as in such as DIN Standard 54900 define.Such as, biodegradable polymer in the environment due to heat, water, air, microorganism and other factors effect first molecular weight can reduce.The reduction of described molecular weight causes the loss of physical property (toughness) and usually can cause fibrous fracture.Once the molecular weight of polymer is enough low, so monomer and oligomer can be fallen by microbial digestion.In aerobic environment, these monomers or oligomer are finally oxidized to CO ₂, H ₂o and new cellular biomass.In anaerobic environment, monomer or oligomer are finally converted into CO ₂, H ₂, acetate, methane and cellular biomass.

Such as, nonaqueous dispersion polymer can be aliphatic-aromatic polyester, is abbreviated as herein " AAPE ".Term used herein " aliphatic-aromatic polyester " represents the polyester of the mixture of the residue comprised from aliphatic or cyclic aliphatic dicarboxylic acids or glycol and aromatic dicarboxylate or glycol.Represent that the carboxyl of described monomer or hydroxyl are not connected by aromatic rings for the term " non-aromatic () " that dicarboxylic acids of the present invention and diol monomer are used herein.Such as, adipic acid in its main chain (namely connecting the carbon atom chain of each hydroxy-acid group) not containing aromatic rings, because of but " non-aromatic ".Relatively, term " aromatics () " represents that dicarboxylic acids or glycol comprise aromatic rings, such as terephthalic acid (TPA) or NDA in main chain.Therefore " non-aromatic () " is intended to comprise aliphatic and cyclo-aliphatic structure, such as comprise its composition straight or branched of carbon atom or cyclic configuration as the glycol of main chain and dicarboxylic acids, described main chain itself can be (namely the comprising carbon carbon triple bond) of saturated or paraffinic, undersaturated (namely comprising non-aromatic carbon-carbon double bond) or acetylene series.Therefore, in the context of description of the present invention and claims, non-aromatic () is intended to comprise chain structure (being called " aliphatic () ") and the circulus (being called " alicyclic () " or " cyclic aliphatic () ") of linear and branching herein herein.But term " non-aromatic () " is not intended to get rid of any aromatic substituent, and it can be connected on the main chain of aliphatic or cycloaliphatic diol or dicarboxylic acids.In the present invention, dicarboxylic acids normally aliphatic dicarboxylic acid (such as adipic acid) or aromatic dicarboxylate's (such as terephthalic acid (TPA)).Dihydroxylic compound can be cycloaliphatic diol (such as Isosorbide-5-Nitrae-cyclohexanedimethanol), the aliphatic diol (such as BDO) of linear or branching or aromatic diol (such as quinhydrones).

AAPE can be the atactic polyester and/or the chain growth copolyesters that comprise the linear of diol residue or branching, described diol residue comprises that one or more are substituted or unsubstituted, the residue of the glycol of linear or branching, and described glycol is selected from the aliphatic diol comprising 2 to about 8 carbon atoms, the polyalkylene ether glycols comprising 2-8 carbon atom and comprises the cycloaliphatic diol of about 4 to about 12 carbon atoms.Usually, described replacement glycol will comprise 1 to about 4 substituting group, each substituting group independent selected from halo, C ₆-C ₁₀aryl and C ₁-C ₄alkoxyl.The example of operable glycol includes but not limited to: ethylene glycol, diethylene glycol, propylene glycol, 1, ammediol, 2, 2-dimethyl-1, ammediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexylene glycol, polyethylene glycol, diethylene glycol, 2, 2, 4-trimethyl-1, 6-hexylene glycol, thiodiethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol, triethylene glycol and TEG, preferred glycol comprises one or more and is selected from following glycol: 1, 4-butanediol, 1, ammediol, ethylene glycol, 1, 6-hexylene glycol, diethylene glycol or 1, 4-cyclohexanedimethanol.AAPE also comprises diacid residues, in the total mole number of diacid residues, it comprises the residue of the non-aromatic dicarboxylic acids of substituted or unsubstituted, the linear or branching of one or more of about 35 to about 99 % by mole, and this non-aromatic dicarboxylic acids is selected from the aliphatic dicarboxylic acid comprising 2 to about 12 carbon atoms and the cycloaliphatic acids comprising about 5 to about 10 carbon atoms.The non-aromatic dicarboxylic acids replaced will comprise 1 to about 4 substituting group usually, and it is selected from halogen, C ₆-C ₁₀aryl and C ₁-C ₄alkoxyl.The limiting examples of non-aromatic diacid comprises malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, decanedioic acid, fumaric acid, 2,2-dimethylated pentanedioic acid, suberic acid, 1,3-ring penta dioctyl phthalate, 1,4-cyclohexyl dicarboxylic acid, 1,3-cyclohexyl dicarboxylic acid, diglycolic acid, itaconic acid, maleic acid and 2,5-norbornane dioctyl phthalate.Unless outside aromatic dicarboxylate, in the total mole number of diacid residues, AAPE also comprises one or more substituted or unsubstituted residues comprising the aromatic dicarboxylate of 6 to about 10 carbon atoms of about 1 to about 65 % by mole.Use in the situation replacing aromatic dicarboxylate wherein, they will comprise 1 to about 4 substituting group usually, and each substituting group is selected from halogen, C ₆-C ₁₀aryl and C ₁-C ₄alkoxyl.The limiting examples of the aromatic dicarboxylate in AAPE used in the present invention is terephthalic acid (TPA), M-phthalic acid, the salt of 5-sulfoisophthalic acid and NDA.More preferably, non-aromatic dicarboxylic acids will comprise adipic acid, and aromatics unit carboxylic acid will comprise terephthalic acid (TPA), and glycol will comprise BDO.

Other possible compositions for AAPE of the present invention are with 100 % by mole of diacid component and 100 % by mole of diol component, such as, prepared by following glycol and the dicarboxylic acids (or its polyester forms equivalent, diester) of following molar percentage those:

(1) glutaric acid (about 30 to about 75%), terephthalic acid (TPA) (about 25 to about 70%), BDO (about 90-100%) and modifying glycol (0 to about 10%);

(2) succinic acid (about 30 to about 95%), terephthalic acid (TPA) (about 5 to about 70%), BDO (about 90-100%) and modifying glycol (0 to about 10%); With

(3) adipic acid (about 30 to about 75%), terephthalic acid (TPA) (about 25 to about 70%), BDO (about 90-100%) and modifying glycol (0 to about 10%).

Modifying glycol is preferably selected from Isosorbide-5-Nitrae-cyclohexanedimethanol, triethylene glycol, polyethylene glycol and neopentyl glycol.Most preferred AAPE is the copolyesters of linear, branching or chain growth, comprises about 50 to about 60 % by mole of adipic acid residues, about 40 to about 50 % by mole of terephthalic acid residues and at least 95 % by mole of BDO residues.Even more preferably, adipic acid residue accounts for about 55 to about 60 % by mole, and terephthalic acid residue accounts for about 40 to about 45 % by mole, and diol residue comprises the BDO residue of about 95 % by mole.This composition commercially can trade mark EASTAR BIO copolyesters available from Eastman Chemical Company, Kingsport, TN and with trade mark ECOFLEX available from BASF Corporation.

In addition, the special example of preferred AAPE comprises: poly-(tetramethylene glutarate-copolymerization-terephthalate), comprise: (a) 50 % by mole of glutaric acid, 50 % by mole of terephthalic acid residues and 100 % by mole of BDO residues; (b) 60 % by mole of glutaric acid, 40 % by mole of terephthalic acid residues and 100 % by mole of BDO residues; Or (c) 40 % by mole of glutaric acid, 60 % by mole of terephthalic acid residues and 100 % by mole of BDO residues; Poly-(tetramethylene succinate-copolymerization-terephthalate), comprises: (a) 85 % by mole of succinic acid residues, 15 % by mole of terephthalic acid residues and 100 % by mole of BDO residues; Or (b) 70 % by mole of succinic acid residues, 30 % by mole of terephthalic acid residues and 100 % by mole of BDO residues; Poly-(EGS-copolymerization-terephthalate), comprises 70 % by mole of succinic acid residues, 30 % by mole of terephthalic acid residues and 100 % by mole of glycol residues; With poly-(tetramethylene adipate ester-copolymerization-terephthalate), comprise (a) 85 % by mole of adipic acid residues, 15 % by mole of terephthalic acid residues and 100 % by mole of BDO residues; Or (b) 55 % by mole of adipic acid residues, 45 % by mole of terephthalic acid residues and 100 % by mole of BDO residues.

AAPE preferably comprises about 10 to about 1000 repetitives, and preferred about 15 to about 600 repetitives.AAPE can have about 0.4 to about 2.0dL/g, or more preferably from about 0.7 to about 1.6dL/g inherent viscosity, it uses the concentration of 60/40 weight ratio solution of 0.5 gram of copolymer/100ml phenol/tetrachloroethanes to record the temperature of 25 DEG C.

AAPE optionally can comprise the residue of branching agent.In the total mole number (depending on that described branching agent comprises carboxyl or hydroxyl) of diacid or diol residue, the molar percentage scope of branching agent is about 0 to about 2 % by mole, preferably about 0.1 to about 1 % by mole, most preferably from about 0.1 to about 5 % by mole.Branching agent preferably has about 50 to about 5000(more preferably from about 92 to about 3000) weight average molecular weight and the degree of functionality of about 3 to about 6.Branching agent can be such as have 3-6 hydroxyl polyalcohol, there is the polybasic carboxylic acid (or ester forms equivalent group) of 3 or 4 carboxyls or there is the esterification residue of the carboxylic acid amounting to 3-6 hydroxyl and carboxyl.In addition, described AAPE branching can be made by adding peroxide in Reaction extrusion process.

Each fragment of nonaqueous dispersion polymer may be different and can any shaping well known by persons skilled in the art or arrange through the shape of cross section of design at slight part.Such as, described sulfonic polyester and nonaqueous dispersion polymer may be used for the bicomponent fiber that preparation has design shape (such as parallel type, " fabric of island-in-sea type ", segmented pie, other configurations that can split off, core-skin type or other configurations well known by persons skilled in the art).Other multicomponent configurations are also fine.Remove row (side) subsequently, the part in " sea " or " fan-shaped " can obtain very thin fiber.The preparation technology of bicomponent fiber also well known to a person skilled in the art.In bicomponent fiber, the content of sulfonic polyester of the present invention can be about 10 to about 90wt%, and is generally used in the skin portion of sheath core fiber.Typically, when using water-insoluble or nonaqueous dispersion polymer, the bi-component obtained or multicomponent fibre can not aqueous dispersions completely.The parallel type combination with remarkable thermal-shrinkage differential can be used to develop spirality crimping.If need curling, usual serration type or clog and be boxly curlingly applicable to a lot of application.If the second polymers compositions is arranged in the core of core-sheath configuration, so optionally stabilisation can be carried out to described core.

Described sulfonic polyester is specially adapted to the fiber with " fabric of island-in-sea type " or " segmented pie " cross section, because they only need neutrality or slightly acidic water (i.e. " soft water ") to disperse, sometimes need the solution containing caustic alkali from multicomponent fibre, remove other aqueous dispersion polymers by contrast.The term " soft water " used in the present invention represents that described glassware for drinking water is no more than 5 grain CaCO ₃/ gallon (1 grain CaCO ₃/ gallon is equivalent to 17.1ppm).Thus, another aspect of the present invention is multicomponent fibre, and it comprises:

Wherein n is the integer in 2 to about 500 scopes; With

(iv) with the total amount of repetitive, the residue with the branched monomer of 3 or more functional groups of 0 to about 20 % by mole, wherein said functional group is hydroxyl, carboxyl or their combination; With

Dicarboxylic acids, glycol, sulfonic polyester, sulfomonomer, branching monomer residues and nonaqueous dispersion polymer are as previously mentioned.For multicomponent fibre, the Tg that sulfonic polyester has at least 57 DEG C is favourable.Described sulfonic polyester can be the blend of single sulfonic polyester or one or more sulfopolyester polymers.Other examples of the glass transition temperature that sulfonic polyester or sulfonic polyester blend can show are: at least 65 DEG C, at least 70 DEG C, at least 75 DEG C, at least 85 DEG C and at least 90 DEG C.Such as, sulfonic polyester can comprise the residue of the diethylene glycol of one or more M-phthalic acids of about 75 to about 96 % by mole or the residue of terephthalic acid (TPA) and about 26 to about 95 % by mole.As mentioned above, the example of nonaqueous dispersion polymer is polyolefin, polyester, polyamide, polyactide, polycaprolactone, Merlon, polyurethane, cellulose esters and polyvinyl chloride.In addition, nonaqueous dispersion polymer can be biodegradable or biodegradable.Such as, nonaqueous dispersion polymer can be foregoing aliphatic-aromatic polyester.

Novel multicomponent fiber of the present invention can by any means preparation in all multi-methods well known by persons skilled in the art.Therefore, the invention provides the technique of the multicomponent fibre for having shaping cross section, comprise: will have the water dispersible sulfonic polyester of glass transition temperature (Tg) of at least 57 DEG C and one or more and described sulfonic polyester immiscible nonaqueous dispersion polymer spinned fiber, described sulfonic polyester comprises:

The residue of (i) one or more dicarboxylic acids;

(ii) with the total amount of repetitive, the residue of at least one sulfomonomer of about 4 to about 40 % by mole, this sulfomonomer has 2 functional groups and one or more sulfo group be connected on aromatics or cyclic aliphatic ring, and wherein said functional group is hydroxyl, carboxyl or their combination;

Wherein n is the integer in 2 to about 500 scopes; With

Wherein said fiber has multiple fragment comprising described nonaqueous dispersion polymer, and the sulfonic polyester that described fragment is namely between fragment is fully kept apart each other, and with the total weight of fiber, described fiber comprises the pigment or filler that are less than 10wt%.Such as, multicomponent fibre can by following preparation: by the melting each polymer flow is imported in a spinning head or extrusion die with multiple points of dispensing line the small fragment or pencil that make described nonaqueous dispersion polymers compositions be formed to be namely between middle described sulfonic polyester fully to keep apart each other in the extruder separated of sulfonic polyester and one or more nonaqueous dispersion polymer.The cross section of this fiber can be that such as segmented pie is arranged or fabric of island-in-sea type is arranged.In another example, sulfonic polyester and one or more nonaqueous dispersion polymer are separately supplied spinneret orifice, then extrudes with core-skin type form, wherein nonaqueous dispersion polymer forms core, and it is fully encapsulated by sulfonic polyester " skin " polymer.In the situation of this concentric fibers, the spinneret orifice of supply " core " polymer is at the center of die orifice exit, and the flow regime strictly controlling core polymer fluid when spinning is to maintain the proper alignment of two kinds of components.Make it possible in fiber cross section, obtain difform core and/or skin to the transformation of spinneret orifice.In another example, the multicomponent fibre of parallel type cross section or configuration can be had by following preparation: separate water dispersible sulfonic polyester and nonaqueous dispersion polymer by spinneret orifice coextrusion, and the polymer flow separated is assembled with substantially identical speed under the face of spinning head thus merges as mix flow using juxtaposition; Or two strands of polymer flows are separated feeding by spinneret orifice with substantially the same speed by (2), spinneret orifice is assembled in spinning head surface, to merge as mix flow using juxtaposition in the surface of spinning head.In both cases, determined by its metering pump speeds, spinneret orifice quantity and spinneret orifice size at the flow velocity merging each polymer flow in position.

Dicarboxylic acids, glycol, sulfonic polyester, sulfomonomer, branching monomer residues and nonaqueous dispersion polymer are as previously mentioned.Sulfonic polyester has the glass transition temperature of at least 57 DEG C.Other examples of the glass transition temperature that sulfonic polyester or sulfonic polyester blend can show are: at least 65 DEG C, at least 70 DEG C, at least 75 DEG C, at least 85 DEG C and at least 90 DEG C.In a kind of example, sulfonic polyester can comprise with the residue of one or more M-phthalic acids of the total amount of sour residue about 50 to about 96 % by mole or terephthalic acid (TPA) with the residue of the sodium of the total amount of sour residue about 4 to about 30 % by mole for sulfoisophthalic acid; With with the residue with the branched monomer of 3 or more functional groups of the total amount of repetitive about 0 to about 20 % by mole, wherein said functional group is hydroxyl, carboxyl or their combination.In another example, sulfonic polyester can comprise the residue of the diethylene glycol of one or more M-phthalic acids of about 75 to about 96 % by mole or the residue of terephthalic acid (TPA) and about 25 to about 95 % by mole.As mentioned above, the example of nonaqueous dispersion polymer is polyolefin, polyester, polyamide, polyactide, polycaprolactone, Merlon, polyurethane and polyvinyl chloride.In addition, nonaqueous dispersion polymer can be biodegradable or biodegradable.Such as, nonaqueous dispersion polymer can be foregoing aliphatic-aromatic polyester.The example of shaping cross section includes but not limited to: fabric of island-in-sea type, parallel type, core-skin type or segmented pie configurations.

In another embodiment of the present invention, provide the technique for the preparation of the multicomponent fibre with shaping cross section, comprise: by least one water dispersible sulfonic polyester and one or more and this sulfonic polyester immiscible nonaqueous dispersion polymer spinning to prepare multicomponent fibre, wherein said multicomponent fibre has multiple territory comprising described nonaqueous dispersion polymer, and the described sulfonic polyester that described territory is namely between territory is fully kept apart each other; Wherein when measuring with the strain rate of 1 rad/sec for 240 DEG C, described water dispersible sulfonic polyester demonstrates and is less than about 12, the melt viscosity of 000 pool; And wherein in the total mole number of diacid or diol residue, described sulfonic polyester comprises the residue of at least one sulfomonomer being less than 25 % by mole; And wherein multicomponent fibre have be less than about 6 dawn/long filament be spun into denier.

Sulfonic polyester used in these multicomponent fibres and nonaqueous dispersion polymer are existing in literary composition before this invention to be discussed.

In another embodiment of the present invention, provide the technique for the preparation of the multicomponent fibre with shaping cross section, comprising:

(A) by least one water dispersible sulfonic polyester and one or more and the immiscible nonaqueous dispersion of described sulfonic polyester polymer-extruded to prepare multicomponent extrudate, wherein said multicomponent extrudate has multiple territory comprising described nonaqueous dispersion polymer, and the described sulfonic polyester that described territory is namely between territory is fully kept apart each other; With

(B) with multicomponent extrudate described in the speed fusion drawn at least about 2000m/min to prepare multicomponent fibre.

The feature of this embodiment of the present invention is also: described technique comprises with at least about 2000m/min, multicomponent extrudate described in the speed fusion drawn of more preferably at least about 3000m/min and most preferably at least 4500m/min.

Usually, once leave spinneret, described fiber, just by the cross-current quenching of air, makes described fiber solidifying thus.Various finishing agent and slurry (sizes) can be applied on fiber at this one-phase.Usually, subsequently the tensile fiber of cooling is wound on take-up spool.Other additive of effective dose can be added, such as emulsifying agent, antistatic additive, bactericide, defoamer, lubricant, heat stabilizer, UV stabilizer etc. in dressing agent.

Optionally, the fibre deformation of drawn (texture) can be made and roll to form loose continuous filament yarn.A this step technology is called spin-draw-distortion in the art.Other embodiment comprises curling or not curling flat filaments (distortion) yarn or chopped fibres.

Subsequently can by dissolving boundary layer or segmented pie and leaving the less long filament of one or more nonaqueous dispersion polymer described or fine-denier fiber and remove described sulfonic polyester.Therefore the invention provides the technique for fine-denier fiber, comprising:

Wherein n is the integer in 2 to about 500 scopes; With

Wherein said fiber has multiple fragment comprising described nonaqueous dispersion polymer, and the described sulfonic polyester that wherein said fragment is namely between fragment is fully kept apart each other; And with the total weight of fiber, described fiber comprises the pigment or filler that are less than 10wt%; With

Typically, described multicomponent fibre and about 25 DEG C to about 100 DEG C, preferably about 50 DEG C of water to about 80 DEG C of temperature contacts the time of about 10 to about 600 seconds, make sulfonic polyester dissipate thus or dissolving.After removing sulfonic polyester, remaining nonaqueous dispersion polymer microfibers will have 1d/f or less, typically 0.5d/f or less, the more generally average fineness of 0.1d/f or less usually.The typical apply of these remaining nonaqueous dispersion polymer microfibers comprises bondedfibre fabric, such as artificial leather, suede, wipes paper and filter medium.The filter medium prepared by these microfibers can be used in filtered air or liquid.Filter medium for liquid is used for including but not limited to: water, body fluid, solvent and hydrocarbon.The ionic nature of sulfonic polyester also causes advantageously poor " solubility " in brine media (such as body fluid).This character is expect personal care product that is flushable or that otherwise throw aside in sanitary sewage system and clean wiping in paper.Selected sulfonic polyester has also been used as the soil redeposition protective agent in dispersant in dye bath and washing cycle process.

In another embodiment of the present invention, provide the technique for the preparation of fine-denier fiber, comprise: at least one water dispersible sulfonic polyester and one or more and this immiscible nonaqueous dispersion polymer of sulfonic polyester are spun to multicomponent fibre, wherein said multicomponent fibre has multiple territory comprising described nonaqueous dispersion polymer, and the described sulfonic polyester that wherein said territory is namely between territory is fully kept apart each other; Wherein said fiber have be less than about 6 dawn/long filament be spun into denier; Wherein measure with the strain rate of 1 rad/sec at 240 DEG C, described water dispersible sulfonic polyester demonstrates and is less than about 12, the melt viscosity of 000 pool; And wherein in the total mole number of diacid or diol residue, described sulfonic polyester comprises the residue of at least one sulfomonomer being less than about 25 % by mole; With make described multicomponent fibre contact to remove described water dispersible sulfonic polyester with water, thus formed fine-denier fiber.

In another embodiment of the present invention, provide the technique for the preparation of fine-denier fiber, comprising:

(A) by least one water dispersible sulfonic polyester and one or more and the immiscible nonaqueous dispersion of described water dispersible sulfonic polyester polymer-extruded to prepare multicomponent extrudate, wherein said multicomponent extrudate has multiple territory comprising described nonaqueous dispersion polymer, and the described sulfonic polyester that wherein said territory is namely between territory is fully kept apart each other;

(B) with multicomponent extrudate described in the speed fusion drawn at least about 2000m/min to form multicomponent fibre; With

(C) make described multicomponent fibre contact with water to remove described water dispersible sulfonic polyester, thus form fine-denier fiber.

The fusion drawn of preferred described multicomponent extrudate is with at least about 2000m/min, more preferably at least about 3000m/min, and most preferably at least the speed of 4500m/min is carried out.

Be suitable for according to the present invention use this kind of sulfomonomer and sulfonic polyester described above.

Remove owing to usually tolerating in hydroentanglement procedure subsequently according to the preferred sulfonic polyester that this uses on the one hand of the present invention, therefore be preferred for removing the water of described sulfonic polyester from multicomponent fibre higher than room temperature, more preferably described water is at least about 45 DEG C, even more preferably at least about 60 DEG C, most preferably at least about 80 DEG C.

In another embodiment of the present invention, another technique for the preparation of nonaqueous dispersion polymer microfibers is provided.Described technique comprises:

A) multicomponent fibre is cut into short multicomponent fibre of cutting;

B) the fibrous raw material of bag is made to contact to prepare fiber-incorporated slurry with water; The fibrous raw material of wherein said bag comprises shortly cuts multicomponent fibre;

C) described fiber-incorporated slurry is heated with the fiber-incorporated slurry of preparation through heating;

D) optionally described fiber-incorporated slurry is mixed in shear zone;

E) from described multicomponent fibre, remove described sulfonic polyester at least partially comprise the slurry mix of sulfopolyester dispersion and nonaqueous dispersion polymer microfibers with preparation; With

F) from this slurry mix, nonaqueous dispersion polymer microfibers is separated.

Described multicomponent fibre can be cut into the random length that can be used in preparing nonwoven articles.In one embodiment of the present invention, multicomponent fibre is cut into the length within the scope of about 1mm to about 50mm.In another embodiment of the present invention, described multicomponent fibre can be cut into the mixture of different length.

The fibrous raw material of described bag can comprise the fiber of any other types that can be used for preparing nonwoven articles.In one embodiment, the fibrous raw material of described bag comprises further and is selected from following at least one fiber: cellulose fibre slurry, glass fibre, polyester fiber, nylon fiber, polyamide fiber, rayon fiber and cellulose ester fiber.

Fibrous for bag raw material and water are mixed with fiber-incorporated slurry.Preferably, for the ease of removing water dispersible sulfonic polyester, water used is soft water or deionized water.Soft water before this invention literary composition is defined.In one embodiment of the present invention, at least one water softener can be used promote remove water dispersible sulfonic polyester from multicomponent fibre.Any water softener as known in the art can be used.In one embodiment, water softener is chelating agent or calcium ion sequestering agent.Available chelating agent or calcium ion sequestering agent are the compounds that each molecule comprises multiple hydroxy-acid group, and the hydroxy-acid group in the molecular structure of wherein chelating agent is opened by 2-6 atom separates.The example of the most frequently used chelating agent is tetrasodium ethylenediamine tetraacetate (EDTA), and each molecular structure comprises 4 polycarboxylic acid moiety, 3, interval atom between adjacent hydroxy-acid group.Polyacrylic acid sodium salt is the example of calcium sequestering agent, and it comprises hydroxy-acid group and is separated by two atoms between each hydroxy-acid group.The sodium salt of maleic acid or butanedioic acid is the example of the most basic chelant compounds.Other examples of available chelating agent comprise and usually there is multiple hydroxy-acid group in the molecular structure and each hydroxy-acid group separates the compound of required distance (2-6 atomic unit), itself and divalence or polyvalent cation (such as calcium ion) produce favourable steric interaction, and described chelating agent is preferentially attached on divalence or polyvalent cation.This compound includes but not limited to: diethylenetriamine pentaacetic acid, Diethylenetriamine-N, N, N ', N ', N ' '-pentaacetic acid, pentaacetic acid, N, N-two (2-(two-(carboxymethyl) is amino) ethyl)-glycine, diethylenetriamine pentaacetic acid, [[(carboxymethyl) imino group] two (ethylenenitrilo)]-tetraacethyl, edetic acid(EDTA), ethylene nitrilo-tetraacethyl, EDTA, free alkali, EDTA free acid, EDTA, hampene (ethylenediamine tetra-acetic acid), versene (ethylenediamine tetra-acetic acid), N, N '-1,2-ethane two base is two-(N-(carboxymethyl) glycine), ethylenediamine tetra-acetic acid, N, N-bis-(carboxymethyl) glycine, nitrilotriacetic acid, trilone A (aminotriacetic acid), α, α ', α ' '-Trimethylamine tricarboxylic acids, three (carboxymethyl) amine, aminotriacetic acid, hampshire NTA acid (nitrilotriacetic acid(NTA)), nitrilo--2,2 ', 2 ' '-triacetic acid, titriplex i (aminotriacetic acid), nitrilotriacetic acid(NTA) and their mixture.

The amount of the water softener needed depends on that water used is at Ca ⁺⁺with the hardness of other multivalent ion aspects.

By fiber-incorporated slurry heating with the fiber-incorporated slurry of preparation through heating.Temperature is enough to from multicomponent fibre, remove a part of sulfonic polyester.In one embodiment of the present invention, fiber-incorporated slurry is heated to the temperature within the scope of about 50 DEG C to about 100 DEG C.Other temperature ranges are about 70 DEG C to about 100 DEG C, about 80 DEG C to about 100 DEG C and about 90 DEG C to about 100 DEG C.

Optionally, fiber-incorporated slurry is mixed in shear zone.Combined amount is enough to disperse from multicomponent fibre and remove a nonaqueous dispersion sulfonic polyester and separated by nonaqueous dispersion polymer microfibers.In one embodiment of the present invention, the sulfonic polyester of 90% is eliminated.In another embodiment, eliminate the sulfonic polyester of 95%, in another embodiment, eliminate the sulfonic polyester of 98% or more.Shear zone can comprise can to provide from multicomponent fibre dispersion and a removing nonaqueous dispersion sulfonic polyester and equipment nonaqueous dispersion polymer microfibers being separated any type of necessary shear action.The example of this equipment includes but not limited to: beater and refiner.

Water dispersible sulfonic polyester in multicomponent fibre disperses with nonaqueous dispersion polymer fiber and is separated the slurry mix producing and comprise sulfopolyester dispersion and nonaqueous dispersion polymer microfibers after contacting with water and be heated.Then by any-mode as known in the art, nonaqueous dispersion polymer microfibers and sulfopolyester dispersion are separated.Such as, slurry mix can be sent by separation equipment (such as screen cloth and filter).Optionally, can by nonaqueous dispersion polymer microfibers washing one or many to remove more water dispersible sulfonic polyester.

The removal of water dispersible sulfonic polyester can be determined by the physical observation to slurry mix.If water dispersible sulfonic polyester major part is removed, so for the water of nonaqueous dispersion polymer microfibers described in rinsing be clarification.If still at removal water dispersible sulfonic polyester, can be so milky for the water of nonaqueous dispersion polymer microfibers described in rinsing.In addition, if water dispersible sulfonic polyester is still retained on nonaqueous dispersion polymer microfibers, in sense of touch, some glues so described microfiber.

Can by the dispersed sulfonic polyester of any means as known in the art recycle-water from sulfopolyester dispersion.

In another embodiment of the present invention, provide nonaqueous dispersion polymer microfibers, it comprises at least one nonaqueous dispersion polymer, and wherein said nonaqueous dispersion polymer microfibers has the equivalent diameter being less than 5 microns and the length being less than 25 millimeters.Described nonaqueous dispersion polymer microfibers is prepared by the previously described technique for the preparation of microfiber.In another aspect of this invention, nonaqueous dispersion polymer microfibers has the equivalent diameter being less than 3 microns and the length being less than 25 millimeters.In another embodiment of the present invention, nonaqueous dispersion polymer microfibers has the equivalent diameter being less than 5 microns or being less than 3 microns.In other embodiments of the present invention, nonaqueous dispersion polymer microfibers can have and is less than 12 millimeters, is less than 10 millimeters, is less than 6.5 millimeters and be less than the length of 3.5 millimeters.Once be separated, the territory in multicomponent fibre or fragment produce nonaqueous dispersion polymer microfibers.

Present invention includes fibre, it comprises water-dispersible fiber as above, multicomponent fibre, fine-denier fiber or nonaqueous dispersion polymer microfibers.Term " fibre " is interpreted as any goods representing and have fiber or like fibrous.The limiting examples of fibre comprises multifilament fiber, yarn, rope, band, fabric, wet-laid fibrous web, dry-laying fiber web, meltblown fiber web, spun-bonded fibre net, hot sticky fiber web, Hydroentangled fiber web, nonwoven web and fabric and their combination; There is one or more fibrolaminar object, such as multilayer nonwoven articles, laminate and by this kind of fibrous composite product, gauze, bandage, diaper, training pant, cotton balls, operation dress and mask, female sanitary towel etc.In addition, nonaqueous dispersion fine-denier fiber can be used in filter for air filtration, liquid filtering, food preparation, medical applications filters and in the filter medium of paper technology and paper product.In addition, fibre can comprise the replacement insert (replacement inserts) for various personal hygiene and cleaning products.Fibre of the present invention can be able to be the adheres of water dispersible or nonaqueous dispersion with other, lamination, attached or be combined.Fibre (such as nonwoven fabric layer) can be adhered on the backing of flexible plastic film or nonaqueous dispersion material (such as polyethylene).This sub-assembly such as can be used as a kind of component of disposable diaper.In addition, fibre can be obtained by following: dispelled by fiber on another matrix to form the combination mixing (assorted) through melt-blown, the spunbond film of design or the height of membrane structure.

Fibre of the present invention comprises bondedfibre fabric or nonwoven web.Bondedfibre fabric is defined as directly to be made up of fiber web and without fabric that is woven or knit operation.Non-woven material to be defined as directly by fiber but not the thread textile constructions of yarn by textile research institute.These fabrics are normally made up of continuous filament yarn or fiber web or batts, by using various combine with technique to strengthen it, this kind of technology includes but not limited to that adhesive combines, tangled by acupuncture or fluid jet and carry out mechanical interlocked, thermal and stitch combines.Such as, multicomponent fibre of the present invention can make fabric by any known preparation process of textile.Can by applying enough power and make multicomponent fibre split or removing sulfonic polyester and leave remaining fine-denier fiber by fiber web is contacted with water the fabric of gained or fiber web are converted into fine-denier fiber net.

Therefore the invention provides the technique for fine-denier fiber net, comprising:

(A) the water dispersible sulfonic polyester of the glass transition temperature (Tg) with at least 57 DEG C is spun to multicomponent fibre with one or more and the immiscible nonaqueous dispersion polymer of described sulfonic polyester, described sulfonic polyester comprises:

Wherein n is the integer in 2 to about 500 scopes; With

(iv) with the total amount of repetitive, the residue with the branched monomer of 3 or more functional groups of 0 to about 20 % by mole, wherein said functional group is hydroxyl, carboxyl or their combination.

Wherein said multicomponent fibre has multiple fragment comprising described nonaqueous dispersion polymer, and the described sulfonic polyester that wherein said fragment is namely between fragment is fully kept apart each other; And with the total weight of fiber, described fiber comprises the pigment or filler that are less than 10wt%; With

(B) by overlapping for the multicomponent fibre of steps A and collect to form nonwoven web; With

(C) make described nonwoven web contact with water to remove described sulfonic polyester, thus form fine-denier fiber net.

In another embodiment of the present invention, provide the technique for fine-denier fiber net, it comprises:

(A) at least one water dispersible sulfonic polyester and one or more and the immiscible nonaqueous dispersion polymer of described sulfonic polyester are spun to multicomponent fibre, described multicomponent fibre has multiple territory comprising described nonaqueous dispersion polymer, and the described sulfonic polyester that wherein said territory is namely between territory is fully kept apart each other; Wherein said fiber have be less than about 6 dawn/long filament be spun into denier; Wherein measure with the strain rate of 1 rad/sec at 240 DEG C, described water dispersible sulfonic polyester demonstrates and is less than about 12, the melt viscosity of 000 pool; And wherein in the total mole number of diacid or diol residue, described sulfonic polyester comprises the residue of at least one sulfomonomer being less than about 25 % by mole;

(B) multicomponent fibre of step (A) is collected to form nonwoven web; With

(A) by polymer-extruded at least one water dispersible sulfonic polyester and one or more and the immiscible nonaqueous dispersion of described sulfonic polyester become multicomponent extrudate, described multicomponent extrudate has multiple territory comprising nonaqueous dispersion polymer, and the described water dispersible sulfonic polyester that wherein said territory is namely between territory is fully kept apart each other;

(B) with multicomponent extrudate described in the speed fusion drawn at least about 2000m/min to form multicomponent fibre;

(C) multicomponent fibre of step (B) is collected to form nonwoven web; With

(D) make described nonwoven web contact with water to remove described sulfonic polyester, thus form fine-denier fiber net.

Described optimal process also comprised the step of the multicomponent fibre of Hydroentangled described nonwoven web before step (C).In the multicomponent fibre that also preferred described hydroentangling step causes, the loss amount of contained sulfonic polyester is less than about 20wt%, and more preferably described loss is less than 15wt%, is most preferably less than 10wt%.In order to contribute to the object of the loss amount reducing sulfonic polyester in hydroentanglement procedure, the water used in this process preferably has the temperature being less than about 45 DEG C, is more preferably less than about 35 DEG C, is most preferably less than about 30 DEG C.The water preferably used in hydroentanglement procedure minimizes to make the loss amount of sulfonic polyester in multicomponent fibre close to room temperature as far as possible.On the contrary, in step (C) process, the removal of sulfopolyester polymer preferably uses the water had at least about 45 DEG C of temperature to carry out, more preferably at least about 60 DEG C, most preferably at least about 80 DEG C.

After Hydroentangled and before step (C), described nonwoven web can experience thermal cure step, described step comprises the temperature be heated to by nonwoven web at least about 100 DEG C, more preferably at least about 120 DEG C.Thermal cure step makes internal fiber Stress Release out and contributes to the stable fiber product of preparation size.Preferably during being again heated to thermal cure step through the material of heat cure its be heated to temperature time, it demonstrate be less than its initial surface area about 5% surface area shrinkage rate.More preferably, shrinkage factor is less than about 2% of initial surface area, and most preferably shrinkage factor is less than about 1%.

Sulfonic polyester used in multicomponent fibre can be arbitrarily described herein those.But preferably when measuring with the strain rate of 1 rad/sec for 240 DEG C, described sulfonic polyester demonstrates the melt viscosity being less than about 6000 pools, and with the total amount of repetitive, it comprises the residue of at least one sulfomonomer being less than about 12 % by mole.The sulfonic polyester of these types herein above in described.

Further, the inventive method preferably includes the step of the described multicomponent fibre that to stretch with the fiber speed of at least 2000m/min, more preferably at least about 3000m/min, even more preferably at least about 4000m/min, most preferably at least about 5000m/min.

In another embodiment of the present invention, the nonwoven articles comprising nonaqueous dispersion polymer microfibers can be prepared.Described nonwoven articles comprises nonaqueous dispersion polymer microfibers and is prepared by the technique being selected from dry-laying process and dry-laying process.Multicomponent fibre and the technique for the preparation of nonaqueous dispersion polymer microfibers had been disclosed in this manual.

In one embodiment of the present invention, in nonwoven articles, comprise the nonaqueous dispersion polymer microfibers of at least 1%.Nonaqueous dispersion polymer microfibers other content in nonwoven articles are: at least 10%, at least 25% and at least 50%.

In another aspect of this invention, nonwoven articles can comprise other fibers of at least one further.Depend on the type of nonwoven articles to be prepared, other fibers described can be any fibers as known in the art.In one embodiment of the present invention, other fibers described can be selected from: cellulose fibre slurry, glass fibre, polyester fiber, nylon fiber, polyamide fiber, rayon fiber, cellulose ester fiber and their mixture.

Described nonwoven articles also can comprise at least one additive further.Additive includes but not limited to: starch, filler and adhesive.Other additives were discussed in other parts of this description.

Usually, the preparation technology that these nonwoven articles prepared by the nonaqueous dispersion microfiber for being made up of multicomponent fibre can be divided into following group: dry-laying, wet-laying and these technique each other or with other combinations without spinning process.

Usually, dry-laying nonwoven articles prepares with designing the staple fibre processing equipment being used for operating dry state fiber.These comprise mechanical technology such as combing, pneumatic technique and other air lay approach.The fabric (i.e. loop bonding non-woven material) also comprising the nonwoven articles prepared by the long filament of tow form in this kind of and be made up of staple fibre and roll extrusion long filament or yarn.Combing be untie, clean and assorted fibre is with for the preparation of the fibroreticulate technique being processed into nonwoven articles further.Described technique primary alignment is kept together as fibroreticulate fiber by mechanical interlocking and the frictional force between fiber and fiber.Carding machine is equipped with the various combinations of one or more cylinder, roller or fixing gyro, one or more doffer or these primary clusterings usually.A kind of example of carding machine is roller card.The nonaqueous dispersion polymer microfibers that combing effect is combing or processes on the carding roller of a series of interworking between combing point.Other types carding machine comprises woolen card, carding machine and random carding machine.Garnetts also can be used in arranging these fibers.

Nonaqueous dispersion polymer microfibers in dry-laying process also can be arranged by air lay.Be directed on collector by these fiber air-flows, described collector can be smooth conveyer belt or roller.

Multicomponent fibre of the present invention can also prepare extrusion molding fiber web.Example comprises spunbond and melt-blown.Extruding technology is for the preparation of spunbond, melt-blown and perforated membrane nonwoven articles.These nonwoven articles are standby with the machine relevant to polymer-extruded method (such as melt spinning, casting film and Extrusion Coating).Then make nonwoven articles contact to remove water dispersible sulfonic polyester with water, preparation comprises the nonwoven articles of nonaqueous dispersion polymer microfibers thus.

In spunbond process, water dispersible sulfonic polyester and nonaqueous dispersion polymer are converted into fabric by following technique: extrude multicomponent filaments, they be orientated fibre bundle or group (groupings), their layerings be placed on conveying silk screen and its interlocking that makes them.The combination interlocked by heat fused, mechanical interlocking, Hydroentangled, chemical adhesion or these techniques is carried out.

Also meltblown fabric has directly been prepared by water dispersible sulfonic polyester and nonaqueous dispersion polymer.Polymer melted is extruded.Once melt is by extrusion cavities, use the blowing of air high temperature immediately.Air stream makes molten polymer drawing-down and solidifies.Then can isolate from air-flow as fibroreticulate multicomponent fibre and suppress between warm-up mill.

Spunbond and melt-blown group technology also can be used to prepare nonwoven articles.

Wet laying process comprises use paper technology and prepares nonwoven articles.These nonwoven articles are standby with the machine relevant with papermaking with pulp fiber (such as beater grinder).Such as, slurry pumping is online to the continuous yarn designing the staple fibre be used in process fluid.

In a kind of embodiment of wet laying process, nonaqueous dispersion polymer microfibers is suspended in water, and guides in building mortion, discharge water by forming net wherein, and fiber laydown is on netting twine.

In another embodiment of wet laying process, nonaqueous dispersion polymer microfibers is dewatered on screen cloth or woven wire, this screen cloth or woven wire when waterpower forming machine starts on dewatering module (suction box, paillon foil and curatures) with the High Rotation Speed up to 1500 ms/min.Then described is fixed on this line, and continues dehydration until solid content is about 20-30%.Then can be also dry by described compacting.

In another embodiment of wet laying process, provide and comprise following technique:

A) optionally, with nonaqueous dispersion polymer microfibers described in water rinse;

B) add water in nonaqueous dispersion polymer microfibers to prepare nonaqueous dispersion polymer microfibers slurry;

C) optionally, other fibers and/or additive are added in nonaqueous dispersion polymer microfibers or slurry; With

D) slurry comprising nonaqueous dispersion polymer microfibers is transferred to wet laid nonwoven district to prepare nonwoven articles.

Step a) in, the number of times of rinsing depends on for the special-purpose selected by described nonaqueous dispersion polymer microfibers.In step b) in, enough water is added in microfiber so that wet laid nonwoven district can be sent to.

Wet laid nonwoven district comprises in this area the arbitrary equipment becoming known for preparing wet laid nonwoven goods.In one embodiment of the present invention, wet laid nonwoven district comprise at least one screen cloth, silk screen or filter screen with from nonaqueous dispersion polymer microfibers slurry except anhydrating.

In another embodiment of the present invention, before transferring to wet laid nonwoven district, mix described nonaqueous dispersion polymer microfibers slurry.

Also fiber web combined process can be used to prepare nonwoven articles.These can be divided into chemistry and physical technology.Chemical bond represents that use is water base and fiber and/or fiber web is combined with solvent based polymer.These adhesives by saturated, dipping, spraying, printing or can be used as foams.Physical bond technique comprises thermal process (such as calendering and hot-air combination) and mechanical technology (such as acupuncture and Hydroentangled).Pin seam or needling process make fibre machinery interlock by some fibre is moved to subvertical position from the position physics close to level.Acupuncture can be undertaken by needing machine.Needing machine comprises usually for net mechanism, needle plate beam (it comprises the needle plate keeping pin), stripper plate, base plate and fabric wrapping mechanism.

It is use the knitting elements or do not have with yarn to the mechanical joining method making fiber web interlock that stitch combines.Stitch includes but not limited in conjunction with the example of machine: Maliwatt, Arachne, Malivlies and Arabeva.

Nonwoven articles can be kept together by following: 1) fiber web or the mechanical fiber in padding combine and interlocking; 2) various fibre fusion technology, comprises the thermoplastic properties using adhesive fiber, use particular polymers and blend polymer; 3) binder fiber, such as starch, casein, cellulose derivative or synthetic resin (such as acrylic latex or polyurethane) is used; 4) powder-stuck adhesive or 5) their combination.Fiber is usually with random fashion deposition, although also can along a direction orientation, then they combine by one of use said method.

Fibre of the present invention can also comprise the layer of one or more water-dispersible fiber, multicomponent fibre or fine-denier fiber further.Described fibrage can be one or more nonwoven fabric layer, the cross-plied fiber layers of loose combination or their combination.In addition, fibre can comprise individual and health care products, such as but not limited to: child care products (such as baby diaper); Children training diaper; Adult care products's (such as adult diaper and adult incontinent pads); Feminine care (such as female sanitary towel, lady's liner and tampon); Wipe paper; Fibrous cleaning products; Medical treatment and operation nursing product (such as medical wipe paper, chiffon, gauze, inspection bedcover, perform the operation mask, operation dress, bandage and wound dressing); Fabric; Elastomeric yarn, wipe paper, band, other protective barrier part and packaging material.Fibre can be used for absorbing fluid or can by various fluid composition pre-wet and for being delivered on the surface by these compositions.The limiting examples of fluid composition comprises detergent, wetting agent, cleaning agent, skin nursing products (such as cosmetics, ointment, medicament, emollient and perfume).Fibre can also comprise various powder and particle to improve absorbability or as delivery vector.The example of powder and particle includes but not limited to: talcum, starch, various water absorbing agent, water dispersible or water cause expanded polymer (such as super-absorbent polymer), sulfonic polyester and polyvinyl alcohol, silica, pigment and microcapsules.According to the needs of application-specific, also can additive be there is, but and nonessential.The example of additive includes but not limited to: oxidation stabilizers, ultraviolet absorber, colouring agent, pigment, opacifier (delustering agent), fluorescent whitening agent, bactericide, disinfectant, cold flow inhibitor, branching agent and catalyst.

Except water dispersible, above-mentioned fibre can be flushable.Term used herein " flushable () " represent can between conventional hygienic in rinse out and introduce in municipal wastewater or house rot system, and obstruction or the blocking of toilet or sewerage can not be caused.

Described fibre may further include the water dispersible film comprising the second aqueous dispersion polymers.Second aqueous dispersion polymers can be identical or different with aforementioned aqueous dispersion polymers used in fiber of the present invention and fibre.In one embodiment, such as, the second aqueous dispersion polymers can be other sulfonic polyester, and it comprises:

(C) one or more diol residue, wherein with the total amount of diol residue, at least 15 % by mole is the polyethylene glycol with following structure:

Wherein n is the integer in 2 to about 500 scopes; With

(D) with the total amount of repetitive, the residue with the branched monomer of 3 or more functional groups of 0 to about 20 % by mole, wherein said functional group is hydroxyl, carboxyl or their combination.Described other sulfonic polyester can with one or more above-mentioned supplementary polyblends to change the character of the fibre obtained.Depend on application, described supplementary polymer can yes or no water dispersible.Described supplementary polymer and described other sulfonic polyester is miscible or immiscible.

Described other sulfonic polyester can comprise the isophthalic acid residues of other concentration, such as about 60 to about 95 % by mole and about 75 to about 95 % by mole.The further example of isophthalic acid residues concentration range is about 70 to about 85 % by mole, about 85 to about 95 % by mole and about 90 to about 95 % by mole.Described other sulfonic polyester can also comprise the diethylene glycol residue of about 25 to about 95 % by mole.The further example of diethylene glycol residue concentration range comprises about 50 to about 95 % by mole, about 70 to about 95 % by mole and about 75 to about 95 % by mole.Described other sulfonic polyester can also comprise the residue of ethylene glycol and/or Isosorbide-5-Nitrae-cyclohexanedimethanol.The typical concentration range of CHDM residue is about 10 to about 75 % by mole, about 25 to about 65 % by mole and about 40 to about 60 % by mole.The typical concentration range of glycol residue is about 10 to about 75 % by mole, about 25 to about 65 % by mole and about 40 to about 60 % by mole.In another embodiment, described other sulfonic polyester comprises the isophthalic acid residues of about 75 to about 96 % by mole and the diethylene glycol residue of about 25 to about 95 % by mole.

According to the present invention, the sulfonic polyester membrane component of described fibre can make single or multiple lift film.Monofilm can by conventional casting film technology preparation.Multilayer film can by preparations such as conventional lamination methods.Described film can have any conventional thickness, but gross thickness is generally about 2 to about 50 Mills.

The layer of one or more above-mentioned water-dispersible fiber can be comprised containing membrane fiber goods.Described fibrage can be one or more nonwoven fabric layer, the cross-plied fiber layers of loose combination or their combination.In addition, above-mentioned individual and health care products can be comprised containing membrane fiber goods.

As previously mentioned, fibre can also comprise various powder and particle to improve absorbability or as delivery vector.Therefore, in one embodiment, fibre of the present invention comprises the powder comprising the 3rd aqueous dispersion polymers, and this polymer can be identical or different with aforesaid aqueous dispersion polymers component.Other examples of powder and particle include but not limited to: talcum, starch, various water absorbing agent, water dispersible or water cause expanded polymer (such as polyacrylonitrile), sulfonic polyester and polyvinyl alcohol, silica, pigment and microcapsules.

In addition to the applications described above, tencel of the present invention and fibre also have much possible purposes.A kind of new opplication comprise by film or bondedfibre fabric melt jet to surface that is smooth, bending or that be shaped to provide protective layer.A kind of this layer can for durable facility provides surface protection in transportation.In destination, before equipment investment is run, sulfonic polyester skin can be washed off.Another embodiment of this general application design can comprise individual's protection goods and think that the coat of some reusable or limited uses or covering provide interim separation layer.For military, decay long filament pattern can make the matrix of melt jet can by these entity grapplings on the exposed surfaces being about to arrive active carbon and chemical absorbent to be sprayed onto before collector.Along with the development threatened, chemical absorbent even can by changing on melt jet to another layer in subsequent operation region.

The intrinsic major advantage of sulfonic polyester easily can remove from aqueous dispersion through flocculation or precipitation or reclaim described polymer by adding ionic portions (i.e. salt).Also additive method (such as pH value regulates, add non-solvent, freezing etc.) can be used.Therefore, even if after successful protective isolator application and when making described polymer become harmful waste, fibre (such as outer cover protective garments) can use conventional scheme (such as burning) to obtain safe handling with much lower volume of throwing aside.

Knownly not dissolve or the sulfonic polyester of drying forms strong adhesive bond to a large amount of matrix, this matrix includes but not limited to; Short fiber oar, cotton, acrylic resin, artificial silk, Lyocell fibers, PLA(polyactide), cellulose acetate, cellulose acetate propionate, polyethylene terephthalate, polybutylene terephthalate (PBT), polytrimethylene terephthalate, cyclohexanedimethanol's diol ester, copolyesters, polyamide (nylon), stainless steel, aluminium, treated polyolefin, PAN(polyacrylonitrile) and Merlon.Therefore, bondedfibre fabric of the present invention can be used as the laminated bonding agent or the adhesive that combine (such as heat, radio frequency (RF), microwave and ultrasonic method) by known technology.All disclose in nearest a lot of patents can RF activation sulfonic polyester transformation.Therefore, except bond property, New Nonwovens fabric of the present invention can have dual or even more multi-functional.Such as, can obtain disposable infant diaper, wherein non-woven material of the present invention serves as the fluid management components of water-responsive adhesive and final sub-assembly simultaneously.

Present invention also offers the technique for water-dispersible fiber, comprising:

(A) water-dispersity polymer composite is heated to the temperature of more than its flow point, wherein said polymer composition comprises:

The residue of (i) one or more dicarboxylic acids;

(ii) with the total amount of repetitive, the residue of at least one sulfomonomer of about 4 to about 40 % by mole, described sulfo group unit has 2 functional groups and one or more metal sulfonate salt group be connected on aromatics or cyclic aliphatic ring, and wherein said functional group is hydroxyl, carboxyl or their combination; With

(iii) one or more diol residue, wherein with the total amount of diol residue, at least 20 % by mole is the polyethylene glycol with following structure:

Wherein n is the integer in 2 to about 500 scopes;

Wherein with the total amount of polymer composition, described polymer composition comprises the pigment or filler that are less than 10wt%; With

(B) melt spinning becomes long filament.

As mentioned above, optionally, can by aqueous dispersion polymers and sulfonic polyester blended.In addition, optionally, can by nonaqueous dispersion polymer and sulfonic polyester blended to prepare blend, make described blend be immiscible blend.Term used herein " flow point " represents that the viscosity of polymer composition allows the temperature extruded by spinneret or extrusion die or process with other forms.Depend on type and the concentration of sulfomonomer, di-carboxylic acid residue can account for about 60 to about 100 % by mole of sour residue.Other examples of the concentration range of di-carboxylic acid residue are: about 60 % by mole to about 95 % by mole and about 70 % by mole to about 95 % by mole.Preferred di-carboxylic acid residue is M-phthalic acid, terephthalic acid (TPA) and 1,4-cyclohexyl dicarboxylic acid, if or use diester, so also have dimethyl terephthalate (DMT), dimethyl isophthalate and 1,4-cyclohexyl dicarboxylic acid dimethyl ester, the especially preferably residue of M-phthalic acid and terephthalic acid (TPA).

Sulfomonomer can be comprise sulfonate groups dicarboxylic acids or its ester, comprise the glycol of sulfonate groups or comprise the carboxylic acid of sulfonate groups.With the total amount of repetitive, other examples of the concentration range of sulfomonomer residue are about 4 to about 25 % by mole, about 4 to about 20 % by mole, about 4 to about 15 % by mole and about 4 to about 10 % by mole.The CATION of sulfonate can be metal ion, such as Li ⁺, Na ⁺, K ⁺, Mg ⁺⁺, Ca ⁺⁺, Ni ⁺⁺, Fe ⁺⁺deng.Selectively, the CATION of sulfonate can be nonmetallic, such as foregoing nitrogenous base.The example that can be used for the sulfomonomer residue in present invention process is sulfosalicylic phthalate, sulfoterephthalic, the metal sulfonate of sulfoisophthalic acid or their combination.Can another example of used sulfomonomer be that 5-sodium is for sulfoisophthalic acid or its ester.If sulfomonomer residue be 5-sodium for sulfoisophthalic acid, so with the total amount of sour residue, typical sulfomonomer concentration range is about 4 about 35 % by mole, about 8 to about 30 % by mole and about 10-25 % by mole.

Sulfonic polyester of the present invention comprises one or more diol residue, and it can comprise aliphatic, cyclic aliphatic and aralkyl glycol.Cycloaliphatic diol (such as 1,3-and Isosorbide-5-Nitrae-cyclohexanedimethanol) as its pure cis or transisomer or can exist as the mixture of cis and transisomer.The limiting examples of the polyethylene glycol of lower molecular weight (such as n is 2-6) is diethylene glycol, triethylene glycol and TEG.In the glycol of these lower molecular weights, most preferably diethylene glycol and triethylene glycol.Sulfonic polyester optionally can comprise branched monomer.The example of branched monomer is described above.Other examples of branching monomer concentration scope are 0 to about 20 % by mole and 0 to about 10 % by mole.The sulfonic polyester of novel process of the present invention has the Tg of at least 25 DEG C.Other examples of the glass transition temperature that sulfonic polyester shows are at least 30 DEG C, at least 35 DEG C, at least 40 DEG C, at least 50 DEG C, at least 60 DEG C, at least 65 DEG C, at least 80 DEG C and at least 90 DEG C.Although other Tg are also fine, the typical glass transition temperature of dry sulfonic polyester of the present invention is about 30 DEG C, about 48 DEG C, about 55 DEG C, about 65 DEG C, about 70 DEG C, about 75 DEG C, about 85 DEG C and about 90 DEG C.

Water-dispersible fiber is prepared by melt-blown process.Described polymer is melted in an extruder and forces it to pass through die head.The extrudate leaving die head passes through the quick drawing-down of high-speed air of heat to ultra micro diameter.The orientation of fiber, cooldown rate, glass transition temperature (Tg) and crystalline rate are important, because their can affect viscosity and the working properties of polymer in drawing-down process.Filament collection is in renewable surface (such as moving conveyor belt, roller, rotary core shaft etc.).Predrying (if need), extruder district temperature, melt temperature, screw design, through-rate, air themperature, air velocity (speed), die head air gap and the set back (retrude) of pill, protuberance tip hole size, die head temperature, die head and collector (DCP) spacing, quenching environment, collector speed and post processing are all affect product feature as filament diameter, basic weight, net thickness, aperture, pliability and inotropic factor.High-speed air can also be used to be moved in slightly random mode by long filament, obtain extensive intertexture.If moving conveyor belt passes through below die head, so can be shelved by the overlap of long filament, the combination of mechanical adhesion and thermal prepares bondedfibre fabric.Also can dispel on another matrix (such as spunbond or back sheet).If by winding filament in rotary core shaft, so form cylindric product.Water-dispersible fiber deposit can also be prepared by spunbond process.

Therefore invention further provides the technique for water dispersible bondedfibre fabric, comprising:

The residue of (i) one or more dicarboxylic acids;

(ii) with the total amount of repetitive, the residue of at least one sulfomonomer of about 4 to about 40 % by mole, described sulfomonomer has 2 functional groups and one or more metal sulfonate salt group be connected on aromatics or cyclic aliphatic ring, and wherein said functional group is hydroxyl, carboxyl or their combination; With

Wherein n is the integer in 2 to about 500 scopes;

Wherein sulfonic polyester has the glass transition temperature (Tg) of at least 25 DEG C; Wherein with the total amount of polymer composition, described polymer composition comprises the pigment or filler that are less than 10wt%;

(B) melt spinning becomes long filament; With

(C) overlapping and collect step (B) long filament to form bondedfibre fabric.

As mentioned above, optionally, can by aqueous dispersion polymers and sulfonic polyester blended.In addition, optionally, can by nonaqueous dispersion polymer and sulfonic polyester blended to prepare blend, make described blend be immiscible blend.Dicarboxylic acids, sulfomonomer and branching monomer residues are as previously mentioned.Sulfonic polyester has the Tg of at least 25 DEG C.Other examples of the glass transition temperature that sulfonic polyester shows are at least 30 DEG C, at least 35 DEG C, at least 40 DEG C, at least 50 DEG C, at least 60 DEG C, at least 65 DEG C, at least 80 DEG C and at least 90 DEG C.Although other Tg are also fine, the typical glass transition temperature of dry sulfonic polyester of the present invention is about 30 DEG C, about 48 DEG C, about 55 DEG C, about 65 DEG C, about 70 DEG C, about 75 DEG C, about 85 DEG C and about 90 DEG C.

In certain embodiments of the invention, in wet laid nonwoven technique that the water-wet microfiber product (wet lapped (wet lap)) prepared after prescinding multicomponent fibre, wash and remove excessive water can be directly used in (namely dry no longer further).In wet laid nonwoven technique, directly use this wet lapped product to avoid the demand of this wet lapped of bone dry, thereby saving a large amount of energy and equipment cost.When wet lapped prepares facility away from facility for the preparation of wet laid nonwoven material, described wet lapped packaging can be prepared position from wet lapped and is transported to non-woven material and prepares position.This wet lapped composition will be further described below.

A kind of embodiment of the present invention relates to the wet lapped composition comprising water and multiple synthetic fiber.Water can account at least 50,55 or 60wt% of wet lapped composition and/or be no more than 90,85 or 80wt%.Synthetic fiber can account at least 10,15 or 20wt% of wet lapped composition and/or be no more than 50,45 or 40wt%.Water and synthetic fiber account at least 95,98 or 99wt% of wet lapped composition altogether.Synthetic fiber can have at least 0.25,0.5 or 1 millimeter and/or be no more than the length of 25,10 or 2 millimeters.Synthetic fiber can have at least 0.1,0.5 or 0.75 micron and/or be no more than the smallest lateral dimension of 10,5 or 2 microns.

The minimum dimension of the fiber that " smallest lateral dimension " used herein expression bow compass method records perpendicular to the slender axles of fiber." maximum transverse size " used herein is the full-size of the fiber recorded perpendicular to the slender axles of fiber with bow compass.Fig. 1 a, 1b and 1c present the method how measuring these sizes at various fiber cross section.In Fig. 1 a, 1b and 1c, " TDmin " is smallest lateral dimension, and " TDmax " is maximum transverse size." bow compass method " used herein represents and measures the method for fiber outer diameter, and the size wherein recorded is the distance between therebetween two the coplanar lines of fiber, the outer surface of fiber on the two sides that wherein each parallel lines contact fiber is substantially relative.All fibres size provided herein (such as length, smallest lateral dimension and maximum transverse size) is all the fiber average-size belonging to particular group.

Described wet lapped composition can comprise further content be at least 10,50 or 100ppmw and/or be no more than 1000,500, the fibre finishing compositions of 250ppmw.In one embodiment, fibre finishing compositions can comprise oil, wax and/or aliphatic acid.In another embodiment, fibre finishing compositions can comprise and is derived from natural aliphatic acid and/or is derived from natural oil.In another embodiment, fibre finishing compositions comprises mineral oil, stearate, sorbitol ester and/or neatsfoot stock.In another embodiment, fibre finishing compositions comprises mineral oil.

Described wet lapped composition can comprise content to be further at least 0.001,0.01 or 0.1 and/or to be no more than the aqueous dispersion polymers of 5,2 or 1wt%.In one embodiment, aqueous dispersion polymers comprises at least one sulfonic polyester.This sulfonic polyester can comprise:

(i) with the total amount of sour residue, the residue of one or more dicarboxylic acids of about 50 to about 96 % by mole, one or more dicarboxylic acids wherein said comprise M-phthalic acid and terephthalic acid (TPA);

(ii) with the total amount of sour residue, the residue of at least one sulfomonomer of about 4 to about 40 % by mole, described sulfomonomer has 2 functional groups and one or more sulfonate groups be connected on aromatics or cyclic aliphatic ring, and wherein said functional group is hydroxyl, carboxyl or their combination; With

(iii) one or more diol residue.

The glass transition temperature (Tg) that described sulfonic polyester can have at least 40 DEG C or at least 50 DEG C, the inherent viscosity of at least 0.2dL/g recorded with the concentration of 0.5 gram of sulfonic polyester/100mL solvent in 40 DEG C of 60/40 parts by weight solution in phenol/tetrachloroethane solvent and the melt viscosities being less than about 12000,8000 or 6000 pools recorded with the strain rate of 1 rad/sec at 240 DEG C.

The nonaqueous dispersion synthetic polymer of described wet lapped composition can be selected from: polyolefin, polyester, copolyesters, polyamide, polyactide, polycaprolactone, Merlon, polyurethane, cellulose esters, acrylic polymer, polyvinyl chloride and their blend.In one embodiment, described nonaqueous dispersion synthetic polymer is selected from: polyethylene terephthalate homopolymers, pet copolymer, polybutylene terephthalate (PBT), polytrimethylene terephthalate, nylon 6, nylon66 fiber and their blend.

The technique preparation of described wet lapped composition by comprising the following steps:

A () preparation comprises the multicomponent fibre of at least one water dispersible sulfonic polyester and one or more and this immiscible nonaqueous dispersion synthetic polymer of sulfonic polyester, wherein said multicomponent fibre have be less than 15dpf be spun into denier;

B described multicomponent fibre is cut into short that length is less than 25 millimeters and cuts multicomponent fibre by ();

C () makes described short multicomponent fibre of cutting contact with washings to remove described sulfonic polyester, thus form the slurry of synthetic fiber in sulfopolyester dispersion, and wherein this sulfopolyester dispersion comprises water and described sulfonic polyester at least partially; With

D () removes described sulfopolyester dispersion at least partially from slurry, thus prepare wet lapped composition.

As mentioned above, described wet lapped composition can be directly used in wet laying process to prepare nonwoven articles.In order to described wet lapped is used in wet laying process, wet lapped composition is prepared place from it and is transported to wet laid nonwoven material sections.Described wet lapped composition can merge in wet laid nonwoven district and/or the next-door neighbour upstream in wet laid nonwoven district and other fibers.Other fibers described can be selected from: cellulose fibre slurry, inorfil, polyester fiber, nylon fiber, Lyocell fibers, polyamide fiber, rayon fiber, cellulose ester fiber and their combination.

As a part for wet laying process, wet lapped composition can merge in wet laid nonwoven district and/or the next-door neighbour upstream in wet laid nonwoven district and dilution water.Dilution water and wet lapped can make to use the amount of at least 50,75,90 or 85 weight portion dilution waters to merge for every a wet lapped.

The present invention is illustrated further by following examples.

Embodiment

All pill samples in room temperature predrying at least 12 hours all under vacuo.Jitter time shown in table 3 is for dispersing or dissolving bondedfibre fabric sample completely.Abbreviation " CE " expression " comparative example " used in table 2 and 3.

Embodiment 1

By Ih.V. for 0.29 and Tg is 48 DEG C comprises 76 % by mole of M-phthalic acids, 24 % by mole of sodium uses the condition melt jet shown in table 1 on cylindrical collector for the sulfonic polyester of sulfoisophthalic acid, 76 % by mole of diethylene glycols and 24 % by mole of Isosorbide-5-Nitrae-cyclohexanedimethanols by nominal 6 inches of die heads (in nozzle 30 holes/inch).Do not need lining paper.Obtain the flexible fibrous web of soft hand-holdable (handleable), do not lump in roller operating winding process.As shown in the data in table 3, in table 2, provide physical property.Under gentle agitation, the small pieces of described bondedfibre fabric (1 " × 3 ") be easily dispersed in room temperature (RT) and 50 DEG C of water.

Table 1-melt jet condition

The physical property of table 2-bondedfibre fabric

The dispersiveness of table 3-bondedfibre fabric

Embodiment 2

Use and similar condition in table 1, Ih.V. is 0.4 and Tg be 35 DEG C comprise 89 % by mole of M-phthalic acids, 11 % by mole of sodium is sprayed by 6 inches of die melt for the sulfonic polyester of sulfoisophthalic acid, 72 % by mole of diethylene glycols and 28 % by mole of ethylene glycol.Obtain soft hand-holdable flexible fibrous web, do not lump in roller operating winding process.Physical property is provided in table 2.As shown in the data in table 3, the small pieces of described bondedfibre fabric (1 " × 2 ") when 50 DEG C and 80 DEG C easily and disperse completely, at RT(23 DEG C) time, fabric needs the longer time to disperse completely.

Find that the composition in embodiment 1 and 2 can dispel in other nonwoven matrix.Silk can also be collected and reel and substitute the shaping of conventional net collector use or the form of special type.Therefore, described fibroreticulate circle " rove " or plunger (plug) form can be obtained.

Comparative example 1-3

Ih.V. is 0.4 and Tg be 35 DEG C comprise 89 % by mole of M-phthalic acids, 11 % by mole of sodium merges with following bi-component ratio (wt%) for the pill of the sulfonic polyester of sulfoisophthalic acid, 72 % by mole of diethylene glycols and 28 % by mole of ethylene glycol and polypropylene (Basell PF 008) pill:

75 PP:25 sulfonic polyesters (embodiment 3)

50 PP:50 sulfonic polyesters (embodiment 4)

25 PP:75 sulfonic polyesters (embodiment 5)

The MFR(melt flow rate (MFR) of PP) be 800.The production line being equipped with 24 inches of wide die heads carries out melt jet operation, to obtain the pliable and tough of hand-holdable softness but non-caking fiber web, there is the physical property provided in table 2.As in table 3 report, the small pieces of bondedfibre fabric (1 " × 4 ") easily decompose.But due to insoluble polypropylene component, described fiber is not complete water dispersible.

Embodiment 3

Use the circular piece (4 " diameter) of the bondedfibre fabric of preparation in embodiment 2 as the adhesive layer between two COTTON FABRIC sheets.Hannifin melting press is used within 30 minutes, two cotton piece to be fused together by the pressure applying 35psig at 200 DEG C.The sub-assembly obtained demonstrates very strong bonding strength.Cotton matrix was just torn up before bonding or combination are lost efficacy.Similar result is have also been obtained with other cellulosicss and PET polyester matrix.Ultra-sonic welding techniques also creates powerful combination.

Comparative example 4

Use 24 " die head will have the PP(Exxon 3356G of 1200 MFR) melt jet obtains flexible bondedfibre fabric, it does not lump and easily launches from roller.Small pieces (1 " × 4 ") do not show any response (do not decompose and do not lose basic weight yet) to water in the water of RT or 50 DEG C during submergence 15 minutes.

Embodiment 4

Laboratory staple fiber spinning production line will comprise the melt temperature melt spinning of homofil at 245 DEG C (473oF) that 82 % by mole of M-phthalic acids, 18 % by mole of sodium are the sulfonic polyester of 55 DEG C for the Tg of sulfoisophthalic acid, 54 % by mole of diethylene glycols and 46 % by mole of Isosorbide-5-Nitrae-cyclohexanedimethanols.Be spun into denier and be about 8d/f.Rolling tube runs into some cakings, but the pH value of the tow of 10 long filaments at 82 DEG C within 10-19 second is dissolve easily not adding in the demineralized water of stirring of 5-6.

Embodiment 5

Will by comprising 82 % by mole of M-phthalic acids, 18 % by mole of sodium respectively for sulfoisophthalic acid, 54 % by mole of diethylene glycols and 46 % by mole 1 on the staple fiber spinning production line of laboratory, the sulfonic polyester (Tg is 55 DEG C) of 4-cyclohexanedimethanol and the homofil melt spinning comprising 91 % by mole of M-phthalic acids, 9 % by mole of sodium obtains for the blend (75:25) of the sulfonic polyester (Tg is 65 DEG C) of sulfoisophthalic acid, 25 % by mole of diethylene glycols and 75 % by mole of Isosorbide-5-Nitrae-cyclohexanedimethanols.Calculated by the weighed average of getting the Tg of sulfonic polyester component, described blend has the Tg of 57 DEG C.The tow of 10 long filaments does not demonstrate any caking on rolling tube, but the pH value at 82 DEG C within 20-43 second is dissolve easily not adding in the demineralized water of stirring of 5-6.

Embodiment 6

Blend described in embodiment 5 and PET co-spun yarn are obtained fabric of island-in-sea type bicomponent fiber.The 20wt% that in the configuration obtained, sulfonic polyester " sea " is fiber, this fiber comprises the PET " island " of 80wt%.Immediately after spinning, the percentage elongation of this spun yarn is 190%.1 week after spinning, when taking off from roll and process this yarn satisfactorily, do not run into caking.In subsequent operation, by making yarn " sea " be dissolved by 88 DEG C of soft water baths, only leave thin PET long filament.

Embodiment 7

This predictive embodiment is may apply for the preparation of speciality paper exemplified with multicomponent of the present invention and fine-denier fiber.By the blend described in embodiment 5 and PET co-spun yarn to obtain fabric of island-in-sea type bicomponent fiber.Described fiber comprises the PET " island " of about 35wt% sulfonic polyester " sea " component and about 65wt%.Not curling fiber is cut into 1/8 inchage.In simulation papermaking, these short-cut bi-component fibers are added in homogenate operation.In the aqueous slurry stirred, eliminate sulfonic polyester " sea ", make micro Denier PET be discharged in mixture thus.When weight is suitable, micro Denier PET (" island ") more effectively improves the TENSILE STRENGTH of paper than adding thick CPT fiber.

Comparative example 8

Use available from Hills Inc. 24 of Melbourne, FL " wide bi-component spinneret die product line of spinning viscose on be prepared in the marine bicomponent fiber with the structure on 108 islands, described die head has 2222 nibs altogether in template.Two extruders are connected to Melt Pump, and Melt Pump is connected to again the entrance of two components in fibre spinning die head.First extruder (A) is connected to form territory, island in islands-in-sea type fibre cross-sectional structure with the entrance of metering Eastman F61HC PET polyester current.Extrude the temperature melting PET entering spinneret die that district is set as at 285 DEG C.Second extruder (B) processing is available from Eastman Chemical Company, Kingsport, the Eastman AQ55S sulfopolyester polymer of TN, described sulfopolyester polymer have about 0.35 inherent viscosity and at Rheometric Dynamic Analyzer RDAII(Rheometrics Inc, Piscataway, New Jersey) record with 240 DEG C and 1 rad/sec shear rate in flow graph about 15,000 pool and 9,700 melt viscosities of mooring recorded at 240 DEG C and 100rad/sec shear rate.Before carrying out measuring melt viscosity, by sample in the vacuum drying oven of 60 DEG C dry 2 days.Viscosimetric analysis uses the parallel-plate shape of 25mm diameter to carry out with the setting of 1mm gap.Dynamic frequency scanning runs with the strain amplitude of the strain rate of 1-400rad/sec and 10%.Then viscosity is measured in the strain rate of 240 DEG C and 1 rad/sec.Follow the viscosity that this operation measures the sulfonic polyester material used in subsequent embodiment.Second extruder is set as, at the melt temperature of 255 DEG C, AQ 55S polymer melting is supplied to spinneret die.By extruding, these two kinds of polymer are formed bi-component extrudate with the through-rate of 0.6g/ hole/min.Regulate the volume ratio of PET and AQ 55S in bi-component extrudate to obtain the ratio of 60/40 and 70/30.

Use inhaler device fusion drawn bi-component extrudate to prepare bicomponent fiber.By the air stream in aspirator chamber by drop-down for obtained fiber.Flowed downward by the air capacity of getter by the Stress control of the air entering aspirator.In this embodiment, be 25psi for the maximum pressure of the air of fusion drawn bi-component extrudate in aspirator.Exceed this value, extrudate can be caused by the air-flow of aspirator to rupture in this fusion drawn spinning process, because the fusion drawn speed be applied on bi-component extrudate is greater than the intrinsic ductility of bi-component extrudate.Bicomponent fiber is laid and becomes the nonwoven web with 95 grams/m of (gsm) fabric weights.By light microscope, the evaluation display PET of bicomponent fiber in this nonwoven web is present in the center of fibre structure as island, but almost coalesce together on the PET island of bicomponent fiber peripheral, define subcontinuous pet polymer ring at the circumference of fiber, this is less desirable.What microscopic analysis found bicomponent fiber in nonwoven web typically has a diameter from 15-19 micron, and the average fiber corresponding to about 2.5 dawn/long filament (dpf) is spun into denier.This represents fusion drawn fiber speed and is about 2160 ms/min.Be spun into denier and be defined through the denier (grammes per square metres of 9000 meters of fibre lengths) melt extruding the fiber obtained with fusion drawn step.The spin-draw of the change list light fibers of bicomponent fiber diameter is uneven.

Nonwoven web sample is regulated 5 minutes at 120 DEG C in forced air draft oven.Show significant contraction through heat treated fiber web, the area of nonwoven web is reduced to about 12% of the initial area being only heating this net front.Be bound by theory although be not meant to, due to high molecular and the melt viscosity of AQ 55S sulfonic polyester used in described fiber, described bi-component extrudate can not degree needed for fusion drawn to the PET fragment generation Strain induced crystallization made in fiber.In general, the AQ 55S sulfonic polyester with described specific inherent viscosity and melt viscosity is unacceptable, because bi-component extrudate can not be stretched to required thin denier by molten homogeneous.

Embodiment 8

Prepare the sulfopolyester polymer with commodity Eastman AQ55S polymer with identical chemical composition, but molecular weight is controlled to lower value, being characterized by inherent viscosity is about 0.25.Measure with 1 rad/sec shear rate at 240 DEG C, the melt viscosity of this polymer is 3300 pools.

Embodiment 9

Use available from Hills Inc. the bi-component spinneret die preparation of Melbourne, FL has the bi-component extrudate of the segmented pie structure of 16 blocks, 24 inches of wide templates on spunbonded equipment has 2222 nibs altogether.Use two extruders by two kinds of polymer meltings and supply this spinneret die.First extruder (A) is connected with the entrance of formative region or fragment thin slice in segmented pie cross-sectional structure with supply Eastman F61HC PET polyester fondant.Extrude the temperature melting PET entering spinneret die that district is set as at 285 DEG C.(B) melting of second extruder also supplies the sulfopolyester polymer of embodiment 8.Second extruder is set as being that the sulfopolyester polymer of 255 DEG C is expressed in spinneret die by melt temperature.Except the melt viscosity of spinneret die used and sulfopolyester polymer, the operation used in the present embodiment is identical with comparative example 8.Melt throughput/hole is 0.6gm/min.In bi-component extrudate, the volume ratio of PET and sulfonic polyester is set as 70/30, and this represents that weight ratio is about 70/30.

Use with bi-component extrudate described in identical aspirator fusion drawn used in comparative example 8 to prepare bicomponent fiber.First, the input air of aspirator is set as 25psi, fiber have about 2.0 be spun into denier, bicomponent fiber demonstrate about 14-15 micron homogeneous diameter distribution.The air of supply aspirator is brought up to maximum allowable pressure 45psi when not making melt extrudate rupture in fusion drawn process.Use 45psi air, bi-component extrudate is by downward fusion drawn to being spun into the fiber that denier is about 1.2, and during observation, bicomponent fiber demonstrates the diameter of 11-12 micron under the microscope.Speed in fusion drawn process is calculated as about 4500m/min.Be bound by theory although be not meant to, when the fusion drawn speed close to this speed, think that PET starts strain inducing crystallization occurs in fusion drawn process.As mentioned above, in fibers melt drawing process, be desirably in the degree of crystallinity forming some orientations in PET fragment, make described nonwoven web have higher DIMENSIONAL STABILITY in process subsequently.

The nonwoven web with 140 grams/m of (gsm) weight is become by using the bicomponent fiber of 45psi aspirator air pressure to lay.By regulating 5 minutes at 120 DEG C in forced air draft oven, measure the shrinkage factor of nonwoven web.This embodiment is compared shrinkage factor with the fiber of comparative example 8 with fabric and is significantly reduced.

The described nonwoven web with 140gsm fabric weight is soaked 5 minutes in the static deionization water-bath of different temperatures.Nonwoven web through soaking is dry, measure owing to soaking the percent weight loss caused in the deionized water of various temperature, be shown in Table 4.

Table 4

Soaking temperature	25℃	33℃	40℃	72℃
					The nonwoven web loss in weight (%)	3.3	21.7	31.4	31.7

About 25 DEG C time, sulfonic polyester is very easy to be dissipated in deionized water.Sulfonic polyester shows as loss in weight % from the removal in the bicomponent fiber nonwoven web.Under 33 DEG C or higher temperature, observe sulfonic polyester remove in a large number or completely from bicomponent fiber.If use Hydroentangled preparation to comprise the nonwoven web of these bicomponent fibers of the sulfopolyester polymer of the present invention of embodiment 8, if so expect that water temperature is room temperature, described sulfopolyester polymer can in a large number or completely remove by Hydroentangled water jet.If need to remove very small amount of sulfopolyester polymer from these bicomponent fibers in hydroentangling step, the low water temperature lower than about 25 DEG C so should be used.

Embodiment 10

Sulfopolyester polymer is prepared: two acid compositions (71mol% terephthalic acid (TPA), 20mol% M-phthalic acid and 9mol% 5-sodium are for sulfoisophthalic acid) and Diol composition (60mol% ethylene glycol and 40mol% diethylene glycol) with following diacid and Diol composition.Sulfonic polyester is prepared by vacuum high-temperature polyesterification.Control enzymatic synthesis condition has the inherent viscosity of about 0.31 sulfonic polyester with preparation.Measure with 1 rad/sec shear rate at 240 DEG C, the melt viscosity of described sulfonic polyester is within the scope of about 3000-4000 pool.

Embodiment 11

According to the operation identical with described in embodiment 9, the sulfopolyester polymer of embodiment 10 is spun to bi-component segmented pie fiber and nonwoven web.First extruder (A) supplies Eastman F61HC PET polyester fondant to form larger fragment thin slice in segmented pie structure.Extrude the temperature melting PET entering spinneret die that district is set as at 285 DEG C.The sulfopolyester polymer of the second extruder (B) process embodiment 10, is supplied to it in spinneret die with the melt temperature of 255 DEG C.Melt throughput/hole is 0.6gm/min.In bi-component extrudate, the volume ratio of PET and sulfonic polyester is set as 70/30, and this represents that weight ratio is about 70/30.The cross section of bi-component extrudate has wedge shape PET territory, and these territories are separated by sulfopolyester polymer.

Use with bi-component extrudate described in identical getter fusion drawn used in comparative example 8 to prepare bicomponent fiber.The maximum allowable pressure supplying the air of aspirator when not making bicomponent fiber rupture in drawing process is 45psi.Use 45psi air, become to be spun into the bicomponent fiber that denier is about 1.2 by bi-component extrudate fusion drawn, during observation, bicomponent fiber demonstrates the diameter of about 11-12 micron under the microscope.Speed in fusion drawn process is calculated as about 4500m/min.

Described bicomponent fiber is laid and becomes the nonwoven web with 140gsm and 110gsm weight.By regulating 5 minutes at 120 DEG C in forced air draft oven, measure the shrinkage factor of nonwoven web.The area of nonwoven web is about 29% of the initial area of described net after contractions.

Demonstrate extraordinary segmented pie structure to the microscopic of cross section of fusion drawn fiber and the fiber of taking from nonwoven web, wherein each segment boundaries is clear and demonstrate similar size and dimension.PET fragment each other completely isolated hold make to remove sulfonic polyester from bicomponent fiber after they can form 8 PET homofils with fan-shaped flake shape separated.

The described nonwoven web with 110gsm fabric weight is soaked 8 minutes in the static deionization water-bath of different temperatures.Nonwoven web through soaking is dry, measure owing to soaking the percent weight loss caused in the deionized water of various temperature, be shown in Table 5.

Table 5

Soaking temperature	36℃	41℃	46℃	51℃	56℃	72℃
							The nonwoven web loss in weight (%)	1.1	2.2	14.4	25.9	28.5	30.5

As shown in the loss in weight, during temperature more than about 46 DEG C, sulfonic polyester is very easy to be dissipated in deionized water, and the temperature sulfopolyester polymer more than 51 DEG C removes in a large number or completely from fiber.The loss in weight of about 30% represents that sulfonic polyester removes completely from the bicomponent fiber nonwoven web.If use Hydroentangled processing to comprise this nonwoven web of the bicomponent fiber of this sulfonic polyester, during the water temperature of expecting below 40 DEG C, described polymer can not be removed in a large number by Hydroentangled water jet.

Embodiment 12

The nonwoven web with 140gsm and 110gsm of hydraulic entangling equipment to embodiment 11 using Fleissner, GmbH, Egelsbach, Germany to manufacture carries out Hydroentangled.Described machine has 5 Hydroentangled stations, the wherein end face of three groups of jet hit nonwoven webs altogether, the another side of two groups of jet hit nonwoven webs.Water jet comprises the pore that the diameter of a series of processing on 2 inches of wide jet bands is about 100 microns.The hydraulic pressure of jet is set as 60 bar (Jet Strip #1), 190 bar (Jet Strip #2 and 3) and 230 bar (Jet Strip #4 and 5).In hydroentanglement procedure, find that the water temperature of jet is within the scope of about 40-45 DEG C.Leave the bondedfibre fabric tangle up securely of hydroentangling apparatus.The entangled generation of continuous fibers has the Hydroentangled bondedfibre fabric of high tear resistance when biaxial tension.

Then, Hydroentangled bondedfibre fabric is fixed to and comprises on the tenter frame of rigid rectangular frame, at rectangle frame peripheral, there is a series of pin.Fabric is fixed on pin to heat limit web contraction.The frame with fabric sample is placed 3 minutes in the forced air draft oven of 130 DEG C, to make the heat cure while limited of described fabric.After heatsetting, the fabric through regulating is cut into the specimen sample of measured size, when limiting without tenter frame by sample 130 DEG C of adjustments.The size of described Hydroentangled bondedfibre fabric after being determined at this adjustment, only observes considerably less contraction (size reduces <0.5%).The heat cure of obvious Hydroentangled bondedfibre fabric is enough to the bondedfibre fabric producing dimensionally stable.

After heat cure described above, Hydroentangled bondedfibre fabric is washed to remove sulfopolyester polymer in 90 DEG C of deionized waters, and PET homofil fragment is retained in Hydroentangled fabric.After repeated washing, dry fabric demonstrates the loss in weight of about 26%.Wash this nonwoven web before Hydroentangled and demonstrate the loss in weight 31.3%.Therefore, hydroentanglement procedure eliminates some sulfonic polyesters from nonwoven web, but this amount is relatively little.In order to reduce the amount of the sulfonic polyester removed in hydroentanglement procedure, the water temperature of Hydroentangled jet should be reduced to lower than 40 DEG C.

Find that the sulfonic polyester of embodiment 10 obtains the segmented pie fiber with good block distributed, wherein after removing sulfopolyester polymer, nonaqueous dispersion polymer segments forms the independently fiber with similar size and dimension.The hexagon of sulfonic polyester is suitable for that described bi-component extrudate is stretched with high-speed molten and obtains having the thin dawn bicomponent fiber being spun into denier being low to moderate about 1.0.These bicomponent fibers can be laid becomes nonwoven web, and described nonwoven web can make bondedfibre fabric through Hydroentangled when not experiencing sulfopolyester polymer significantly loses.Nonwoven web demonstrates higher intensity through the Hydroentangled bondedfibre fabric made, and can produce the bondedfibre fabric with superior dimensional stability at about 120 DEG C or higher temperature heat cure.In washing step, sulfopolyester polymer is removed from Hydroentangled bondedfibre fabric.Obtain the firmly nonwoven products with lighter fabric weight, much higher pliability and more soft feel like this.One pack system PET in this nonwoven products is wedge shape and demonstrates the average denier of about 0.1.

Embodiment 13

Sulfopolyester polymer is prepared: two acid compositions (69mol% terephthalic acid (TPA), 22.5mol% M-phthalic acid and 8.5mol% 5-sodium are for sulfoisophthalic acid) and Diol composition (65mol% ethylene glycol and 35mol% diethylene glycol) with following diacid and Diol composition.Sulfonic polyester is prepared by vacuum high-temperature polyesterification.Control enzymatic synthesis condition has the inherent viscosity of about 0.33 sulfonic polyester with preparation.Measure with 1 rad/sec shear rate at 240 DEG C, the melt viscosity of described sulfonic polyester is within the scope of about 3000-4000 pool.

Embodiment 14

The sulfopolyester polymer of embodiment 13 is spun on product line of spinning viscose the bi-component fabric of island-in-sea type cross sectional configuration with 16 islands.First extruder (A) supplies Eastman F61HC PET polyester fondant to form island in island type structure.Extrude the temperature melting PET entering spinneret die that district is set as at about 290 DEG C.The sulfopolyester polymer of the second extruder (B) process embodiment 13, is supplied to it in spinneret die with the melt temperature of about 260 DEG C.In bi-component extrudate, the volume ratio of PET and sulfonic polyester is set as 70/30, and this represents that weight ratio is about 70/30.By the melt through-rate of spinning head be 0.6g/ hole/minute.The cross section of bi-component extrudate has territory, circular PET island, and these territories are separated by sulfopolyester polymer.

Use bi-component extrudate described in getter fusion drawn.The maximum allowable pressure supplying the air of aspirator when not making bicomponent fiber rupture in fusion drawn process is 50psi.Use 50psi air, become to be spun into the bicomponent fiber that denier is about 1.4 by downward for bi-component extrudate fusion drawn, during observation, bicomponent fiber demonstrates the diameter of about 12 microns under the microscope.Speed in drawing process is calculated as about 3900m/min.

Embodiment 15

Bi-component extruding production line is used the sulfopolyester polymer of embodiment 13 to be spun to the bi-component fabric of island-in-sea type cross section fibres with 64 island fibers.First extruder supply Eastman F61HC polyester fondant to form island in islands-in-sea type fibre cross-sectional structure.Second extruder supply sulfopolyester polymer melt to form sea in fabric of island-in-sea type bicomponent fiber.The inherent viscosity of polyester is 0.61dL/g, and uses aforementioned measuring melt viscosity operation to measure at 240 DEG C with 1 rad/sec strain rate, and the melt viscosity of dry sulfonic polyester is about 7000 pools.These fabric of island-in-sea type bicomponent fibers use the spinning head with the through-rate of 198 holes and 0.85gms/ minutes/well to prepare.Polymer between " island " polyester and " sea " sulfonic polyester is than being 65%:35%.By these bicomponent fiber spinning, polyester components is used to the extrusion temperature of 280 DEG C, sulfonic polyester component is used to the extrusion temperature of 260 DEG C.Described bicomponent fiber comprises multiple long filament (198 long filaments), and with the speed melt spinning of about 530 ms/min, forms the long filament with the nominal denier/long filament of about 14.Kiss roll spreader is used the finish solution of the 24wt% of PT 769 finishing agent available from Goulston Technologies to be applied on bicomponent fiber.Then use one group two godet rollers being heated to 90 DEG C and 130 DEG C respectively by the long filament linear stretch of bicomponent fiber, final draw roll is with the speed operation of about 1750 ms/min, to provide the filament draw ratio of about 3.3 times, form the fabric of island-in-sea type bicomponent filament with the drawn of the nominal denier/long filament of about 4.5 or the average diameter of about 25 microns.These long filaments comprise the polyester microfiber " island " that average diameter is 2.5 microns.

Embodiment 16

The fabric of island-in-sea type bicomponent fiber of the drawn of embodiment 15 is cut into the short length fiber that Cutting Length is 3.2 millimeters and 6.4 millimeters, and preparation has the short length bicomponent fiber of the fabric of island-in-sea type cross-sectional configuration on 64 islands thus.These short-cut bi-component fibers comprise polyester " island " and water dispersible sulfopolyester polymer " sea ".Island is substantially consistent along the length of these short-cut bi-component fibers with the cross-sectional distribution in sea.

Embodiment 17

The fabric of island-in-sea type bicomponent fiber of the drawn of embodiment 15 is soaked 24 hours in soft water, is then cut into the short length fiber that Cutting Length is 3.2 millimeters and 6.4 millimeters.Before being cut into short length fiber, make at least part of emulsification of water dispersible sulfonic polyester.Therefore realize island to be separated from the part sea component, prepare the short length fabric of island-in-sea type bicomponent fiber of part emulsification thus.

Embodiment 18

The soft water of the fabric of island-in-sea type bicomponent fiber of the chopped length of embodiment 16 with 80 DEG C is washed with sulfonic polyester " sea " component removing water dispersible, discharges the polyester microfiber of " island " component as bicomponent fiber thus.Polyester microfiber through washing uses the soft water rinsing of 25 DEG C substantially to remove most " sea " component.Optical microscope inspection display average diameter through the polyester microfiber of washing is about 2.5 microns, and length is 3.2 and 6.4 millimeters.

Embodiment 19

The soft water of the fabric of island-in-sea type bicomponent fiber of the part emulsification of the chopped length of embodiment 17 with 80 DEG C is washed with sulfonic polyester " sea " component removing water dispersible, discharges the polyester microfiber of " island " component as bicomponent fiber thus.Polyester microfiber through washing uses the soft water rinsing of 25 DEG C substantially to remove most " sea " component.Average diameter through the optical microscope inspection display polyester microfiber of the polyester microfiber of washing is about 2.5 microns, and length is 3.2 and 6.4 millimeters.

Comparative example 20

Following operation is used to prepare wet-laying handsheet.By 7.5gm available from International Paper, the Albacel Southern Bleached Softwood Kraft(SBSK of Memphis, Tennesee, U.S.A.) and the room temperature water of 188gm be placed in 1000ml beater, and pull an oar 30 seconds with 7000rpm, to prepare paste mixture.This paste mixture is transferred to together with 7312gm room temperature water in 8 liters of metal beaker to prepare the slurry of about 0.1% concentration (7500gm water and 7.5gm fibrous material).Use quick runner formula mixer by described slurry agitation 60 seconds.The operation being prepared handsheet by this slurry is as follows.By in described slurry impouring 25 cm x 30 centimetres of handsheet moulds, Keep agitation simultaneously.Pull drop valve, pulp fiber is dewatered on screen cloth and forms handsheet.The blotting paper of 750 grams/m (gsm) is placed on above formed handsheet, blotting paper is flattened on handsheet.Raise screen frame and be inverted in clean release liners, making it leave standstill 10 minutes.Screen cloth is vertically risen and leaves formed handsheet.The blotting paper of two panels 750gsm is placed on formed handsheet.Use Norwood Dryer at about 88 DEG C by described handsheet together with described three blotting paper dry 15 minutes.Remove a blotting paper, the every side on handsheet leaves a blotting paper.Use Williams Dryer 65 DEG C of dry handsheets 15 minutes.Then use 40kg dry press by further for handsheet dry 12-24 hour.Removing blotting paper obtains the handsheet sample done.Described handsheet is trimmed to 21.6 cm x 27.9 cm sizes for test.

Comparative example 21

Following operation is used to prepare wet-laying handsheet.By 7.5gm available from International Paper, Memphis, Tennesee, U.S.A. Albacel Southern Bleached Softwood Kraft(SBSK), 0.3gm is available from Avebe, Foxhol, the Solivitose N pregelatinization quaternary ammonium salt cationic potato starch of the Netherlands and the room temperature water of 188gm are placed in 1000ml beater, and pull an oar 30 seconds with 7000rpm, to prepare paste mixture.This paste mixture is transferred to together with 7312gm room temperature water in 8 liters of metal beaker to make concentration for about 0.1%(7500gm water and 7.5gm fibrous material) to prepare slurry.Use quick runner formula mixer by described slurry agitation 60 seconds.All the other operations being prepared handsheet by this slurry are identical with embodiment 20.

Embodiment 22

Following operation is used to prepare wet-laying handsheet.By 6.0gm available from International Paper, Memphis, Tennesee, U.S.A. Albacel Southern Bleached Softwood Kraft(SBSK), 0.3gm is available from Avebe, Foxhol, the Solivitose N pregelatinization quaternary ammonium salt cationic potato starch of the Netherlands, the islands-in-sea type fibre of 3.2 millimeters of Cutting Lengths of 1.5gm embodiment 16 and the room temperature water of 188gm are placed in 1000ml beater, and pull an oar 30 seconds with 7000rpm, to prepare fiber-incorporated slurry.This fiber-incorporated slurry is heated to 82 DEG C keep 10 seconds, with emulsification and removing islands-in-sea type fibre in water dispersible sulfonic polyester component and discharge polyester microfiber.Then described fiber-incorporated slurry is filtered (strained) to prepare the sulfopolyester dispersion comprising sulfonic polyester and the mixture containing microfiber comprising pulp fiber and polyester microfiber.Use the further rinsing of 500gm room temperature water to remove water dispersible sulfonic polyester further from containing in the mixture of microfiber in the described mixture containing microfiber.The mixture that this contains microfiber is transferred in 8 liters of metal beaker to make concentration for about 0.1%(7500gm water and 7.5gm fibrous material together with 7312gm room temperature water) to prepare the slurry containing microfiber.Use quick runner formula mixer by the described slurry agitation containing microfiber 60 seconds.All the other operations preparing handsheet by this slurry containing microfiber are identical with embodiment 20.

Comparative example 23

Following operation is used to prepare wet-laying handsheet.By 7.5gm available from Johns Manville, Denver, Colorado, U.S.A. the micro-glass fibre of MicroStrand 475-106,0.3gm are available from Avebe, Foxhol, the Solivitose N pregelatinization quaternary ammonium salt cationic potato starch of the Netherlands and the room temperature water of 188gm are placed in 1000ml beater, and pull an oar 30 seconds with 7000rpm, to prepare mixture of glass fibers.This mixture of glass fibers is transferred to together with 7312gm room temperature water in 8 liters of metal beaker to make concentration for about 0.1%(7500gm water and 7.5gm fibrous material) to prepare glass fibre slurry.Use quick runner formula mixer by this glass fibre slurry agitation 60 seconds.All the other operations being prepared handsheet by this glass fibre slurry are identical with embodiment 20.

Embodiment 24

Following operation is used to prepare wet-laying handsheet.By 3.8gm available from Johns Manville, Denver, Colorado, the islands-in-sea type fibre of the micro-glass fibre of MicroStrand 475-106 U.S.A., 3.2 millimeters of Cutting Lengths of 3.8gm embodiment 16,0.3gm are available from Avebe, Foxhol, the Solivitose N pregelatinization quaternary ammonium salt cationic potato starch of the Netherlands and the room temperature water of 188gm are placed in 1000ml beater, and pull an oar 30 seconds with 7000rpm, to prepare fiber-incorporated slurry.This fiber-incorporated slurry is heated to 82 DEG C to keep 10 seconds, discharges polyester microfiber with the water dispersible sulfonic polyester component in emulsification and removing fabric of island-in-sea type bicomponent fiber.Then described fiber-incorporated slurry is filtered to prepare the sulfopolyester dispersion comprising sulfonic polyester and the mixture containing microfiber comprising glass micro-fibers peacekeeping polyester microfiber.Use the further rinsing of 500gm room temperature water to remove sulfonic polyester further from containing in the mixture of microfiber in the described mixture containing microfiber.The mixture that this contains microfiber is transferred in 8 liters of metal beaker to make concentration for about 0.1%(7500gm water and 7.5gm fibrous material together with 7312gm room temperature water) to prepare the slurry containing microfiber.Use quick runner formula mixer by this slurry agitation 60 seconds containing microfiber.All the other operations preparing handsheet by this slurry containing microfiber are identical with embodiment 20.

Embodiment 25

Following operation is used to prepare wet-laying handsheet.By the islands-in-sea type fibre of 3.2 of 7.5gm embodiment 16 millimeters of Cutting Lengths, 0.3gm available from Avebe, Foxhol, the Solivitose N pregelatinization quaternary ammonium salt cationic potato starch of the Netherlands and the room temperature water of 188gm are placed in 1000ml beater, and pull an oar 30 seconds with 7000rpm, to prepare fiber-incorporated slurry.This fiber-incorporated slurry is heated to 82 DEG C keep 10 seconds, with emulsification and removing islands-in-sea type fibre in water dispersible sulfonic polyester component and discharge polyester microfiber.Then described fiber-incorporated slurry is filtered to prepare sulfopolyester dispersion and polyester microfiber.Described sulfopolyester dispersion is made up of water dispersible sulfonic polyester.Use the further rinsing of 500gm room temperature water to remove sulfonic polyester further from polyester microfiber described polyester microfiber.These polyester microfiber are transferred to together with 7312gm room temperature water in 8 liters of metal beaker to make concentration for about 0.1%(7500gm water and 7.5gm fibrous material) to prepare microfiber slurry.Use quick runner formula mixer that this microfiber slurry is stirred 60 seconds.All the other operations being prepared handsheet by this microfiber slurry are identical with embodiment 20.

Test the handsheet sample of embodiment 20-25, character provides in the following table.

Handsheet basic weight is determined by weigh handsheet calculated weight (gram)/square metre (gsm).Handsheet thickness uses Ono Sokki EG-233 thickness gauge to record, and is reported to thickness (millimeter).Density calculation is weight (g)/cubic centimetre.Porosity uses Greiner Porosity Manometer to record, and it has square openings end and the 100cc capacity of 1.9 × 1.9cm.Porosity is reported to the average time (second) (4 repeating test) of 100cc water by described sample.Tensile property uses Instron Model TM to record six 30mm × 105mm testing bars.Each embodiment is reported to the mean value measured for six times.Can observe from these test datas by adding polyester microfiber of the present invention, the tensile property of wet laid fibrous structure significantly improves.

Embodiment 26

Bi-component extruding production line is used the sulfopolyester polymer of embodiment 13 to be spun to the bi-component fabric of island-in-sea type cross section fibres with 37 island fibers.First extruder supply Eastman F61HC polyester is to form " island " in fabric of island-in-sea type cross-sectional structure.Second extruder supply water dispersible sulfopolyester polymer is to form " sea " in fabric of island-in-sea type bicomponent fibers.The inherent viscosity of polyester is 0.61dL/g, and uses aforementioned measuring melt viscosity operation to measure at 240 DEG C with 1 rad/sec strain rate, and the melt viscosity of dry sulfonic polyester is about 7000 pools.These fabric of island-in-sea type bicomponent fibers use the spinning head with the through-rate of 72 holes and 1.15gms/ minutes/well to prepare.Mol ratio between " island " polyester and " sea " sulfonic polyester is 2:1.By these bicomponent fiber spinning, polyester components is used to the extrusion temperature of 280 DEG C, water dispersible sulfonic polyester component is used to the extrusion temperature of 255 DEG C.This bicomponent fiber comprises multiple long filament (198 long filaments), and with the speed melt spinning of about 530 ms/min, forms the long filament with the nominal denier/long filament of 19.5.Kiss roll spreader is used the finish solution of the 24wt% of PT 769 finishing agent available from Goulston Technologies to be applied on bicomponent fiber.Then use one group two godet rollers being heated to 95 DEG C and 130 DEG C respectively by bicomponent fiber long filament linear stretch, final draw roll is with the speed operation of about 1750 ms/min, to provide the filament draw ratio of about 3.3 times, form the fabric of island-in-sea type bicomponent filament with the drawn of the nominal denier/long filament of about 5.9 or the average diameter of about 29 microns.These long filaments comprise the polyester microfiber island that average diameter is 3.9 microns.

Embodiment 27

The fabric of island-in-sea type bicomponent fiber of the drawn of embodiment 26 is cut into the short length bicomponent fiber of 3.2 millimeters and 6.4 millimeters Cutting Lengths, preparation has the short length fiber of the fabric of island-in-sea type cross-sectional configuration on 37 islands thus.These fibers comprise polyester " island " and water dispersible sulfopolyester polymer " sea "." island " is substantially consistent along the length of these bicomponent fibers with the cross-sectional distribution in " sea ".

Embodiment 28

The soft water of the chopped length islands-in-sea type fibre of embodiment 27 with 80 DEG C is washed to remove water dispersible sulfonic polyester " sea " component, discharges the polyester microfiber of " island " component as bicomponent fiber thus.Polyester microfiber through washing uses the soft water rinsing of 25 DEG C substantially to remove most " sea " component.Optical microscope inspection display average diameter through the polyester microfiber of washing is about 3.9 microns, and length is 3.2 and 6.4 millimeters.

Embodiment 29

Bi-component extruding production line is used the sulfopolyester polymer of embodiment 13 to be spun to the bi-component fabric of island-in-sea type cross section fibres with 37 island fibers.First extruder supply polyester is to form " island " in islands-in-sea type fibre cross-sectional structure.Second extruder supply water dispersible sulfopolyester polymer is to form " sea " in fabric of island-in-sea type bicomponent fiber.The inherent viscosity of polyester is 0.52dL/g, and uses aforementioned measuring melt viscosity operation to measure at 240 DEG C with 1 rad/sec strain rate, and the melt viscosity of the dispersed sulfonic polyester of solid carbon dioxide is about 3500 pools.These fabric of island-in-sea type bicomponent fibers use two spinning heads of the through-rate separately with 175 holes and 1.0gms/ minutes/well to prepare.Polymer between " island " polyester and " sea " sulfonic polyester is than being 70%:30%.By these bicomponent fiber spinning, polyester components is used to the extrusion temperature of 280 DEG C, water dispersible sulfonic polyester component is used to the extrusion temperature of 255 DEG C.Described bicomponent fiber comprises multiple long filament (350 long filaments), and uses the take up roll being heated to 100 DEG C with the speed melt spinning of about 1000 ms/min, forms the long filament with the nominal denier/long filament of about 9 and the fiber diameter of about 36 microns.Kiss roll spreader is used the finish solution of the 24wt% of PT 769 finishing agent to be applied on bicomponent fiber.Then the long filament of bicomponent fiber is merged, then on stretching production line with the temperature tensile 3.0 times of the draw roll speed of 100m/ minute and 38 DEG C, form the fabric of island-in-sea type bicomponent filament with the drawn of the average denier/long filament of about 3 and the average diameter of about 20 microns.The fabric of island-in-sea type bicomponent filament of these drawns is cut into the short length fiber of about 6.4 mm lengths.The polyester microfiber " island " that the fabric of island-in-sea type bicomponent fiber of these short length is about 2.8 microns by average diameter is formed.

Embodiment 30

The soft water of the chopped length islands-in-sea type fibre of embodiment 29 with 80 DEG C is washed to remove water dispersible sulfonic polyester " sea " component, discharges the polyester microfiber of " island " component as described fiber thus.Polyester microfiber through washing uses the soft water rinsing of 25 DEG C substantially to remove most " sea " component.Average diameter through the optical microscope inspection display polyester microfiber of the fiber of washing is about 2.8 microns, and length is about 6.4 millimeters.

Embodiment 31

Following operation is used to prepare wet-laying raw microfiber handsheet.By the fabric of island-in-sea type bicomponent fiber of 3.2 of 56.3gm embodiment 16 millimeters of Cutting Lengths, 2.3gm available from Avebe, Foxhol, the Solivitose N pregelatinization quaternary ammonium salt cationic potato starch of the Netherlands and the room temperature water of 1410gm are placed in 2 liters of beakers, to prepare fibre stuff.Fibre stuff is stirred.This fibre stuff (about 352ml) of 1/4th amounts is put into 100ml beater and pulls an oar 30 seconds with 7000rpm.This fibre stuff is heated to 82 DEG C to keep 10 seconds, discharges polyester microfiber with the water dispersible sulfonic polyester component in emulsification and removing fabric of island-in-sea type bicomponent fiber.Then described fibre stuff is filtered to prepare sulfopolyester dispersion and polyester microfiber.These polyester microfiber use the rinsing of 500gm room temperature water to remove sulfonic polyester further from polyester microfiber.Add enough room temperature waters to prepare 352ml microfiber slurry.This microfiber slurry is pulled an oar 30 seconds with 7000rpm again.These microfibers are transferred in 8 liters of metal beaker.The fibre stuff of residue 3/4ths is pulled an oar equally, washs, rinsing and again pull an oar and transfer in described 8 liters of metal beaker, then add 6090gm room temperature water to make concentration for about 0.49%(7500gm water and 36.6gm polyester microfiber) to prepare microfiber slurry.Use quick runner formula mixer that this microfiber slurry is stirred 60 seconds.All the other operations being prepared handsheet by this microfiber slurry are identical with embodiment 20.Raw microfiber (stock) handsheet with about 490gsm basic weight is made up of the polyester microfiber of the average length of the average diameter and about 3.2 millimeters with about 2.5 microns.

Embodiment 32

Following operation is used to prepare wet-laying handsheet.By the polyester microfiber raw material handsheet of 7.5gm embodiment 31,0.3gm available from Avebe, Foxhol, the Solivitose N pregelatinization quaternary ammonium salt cationic potato starch of the Netherlands and the room temperature water of 188gm are placed in 1000ml beater, pull an oar 30 seconds with 7000rpm.Described microfiber is transferred to together with 7312gm room temperature water in 8 liters of metal beaker to make concentration for about 0.1%(7500gm water and 7.5gm fibrous material) to prepare microfiber slurry.Use quick runner formula mixer that this microfiber slurry is stirred 60 seconds.All the other operations being prepared handsheet by this slurry are identical with embodiment 20.Obtain having the 100gsm wet-laying handsheet of the polyester microfiber of the average diameter of about 2.5 microns.

Embodiment 33

The soft water of the fabric of island-in-sea type bicomponent fiber of 6.4 of embodiment 29 millimeters of Cutting Lengths with 80 DEG C is washed with sulfonic polyester " sea " component removing water dispersible, discharges the polyester microfiber of " island " component as bicomponent fiber thus.Polyester microfiber through washing uses the soft water rinsing of 25 DEG C substantially to remove most " sea " component.Optical microscope inspection display average diameter through the polyester microfiber of washing is about 2.5 microns, and length is 6.4 millimeters.

Embodiment 34

The chopped length fabric of island-in-sea type bicomponent fiber of embodiment 16, embodiment 27 and embodiment 29 is washed with the soft water of 80 DEG C to remove water dispersible sulfonic polyester " sea " component respectively, discharge the polyester microfiber of " island " component as bicomponent fiber thus, wherein said soft water comprise with the weighing scale of bicomponent fiber be about 1wt% available from Sigma-Aldrich Company, tetrasodium salt of EDTA (the Na of Atlanta, Georgia ₄eDTA).At least one water softener (such as Na ₄being added with EDTA) helps remove water dispersible sulfopolyester polymer from fabric of island-in-sea type bicomponent fiber.Polyester microfiber through washing uses the soft water rinsing of 25 DEG C substantially to remove most " sea " component.The release that the optical microscope inspection of polyester microfiber through washing demonstrates polyester microfiber be separated very good.Water softener (such as Na is used in water ₄eDTA) prevent, on sulfonic polyester, any Ca occurs ⁺⁺ion-exchange, it adversely can affect the water dispersible of sulfonic polyester.Typical soft water can comprise the Ca being no more than 15ppm ⁺⁺ion concentration.Expect the soft water used in the process should have substantially be 0 Ca ⁺⁺with the concentration of other multivalent ions or water softener (the such as Na selectively using q.s ₄eDTA) with in conjunction with these Ca ⁺⁺ion and other multivalent ions.These polyester microfiber can be used in using the operation of previous embodiment to prepare wet-laying handsheet.

Embodiment 35

Use the chopped length fabric of island-in-sea type bicomponent fiber of following operation difference process embodiment 16 and embodiment 27.17 grams of Solivitose N pregelatinization quaternary ammonium salt cationic potato starches available from Avebe, Foxhol, the Netherlands are added in distilled water.After described starch dissolves completely or is hydrolyzed, 429 grams of chopped length fabric of island-in-sea type bicomponent fibers are slowly added in described distilled water to prepare fibre stuff.Open Williams Rotary Continuous Feed Refiner(5 inch diameter) with homogenate or mix this fibre stuff, separate for making water dispersible sulfonic polyester and polyester microfiber to provide enough shear actions.By in content impouring 24 liters of rustless steel containers of stock tank, cover lid.Rustless steel container is placed on propane cooker and heats, until fibre stuff comes to life at about 97 DEG C, to remove the sulfonic polyester component in islands-in-sea type fibre, and discharge polyester microfiber.After fibre stuff reaches boiling, with hand operated mixing oar, it is stirred.The content impouring of rustless steel container is had in the dark False Bottom Knuche of the 27in × 15in × 6in of 30 eye mesh screens, to prepare sulfopolyester dispersion and polyester microfiber.Described sulfopolyester dispersion comprises water and water dispersible sulfonic polyester.In Knuche with the soft water of 10 liters 17 DEG C by polyester microfiber rinsing 15 seconds, and extruding to remove excessive water.

20 grams of polyester microfiber (with dry fiber for benchmark) are added in the water of 2000ml 70 DEG C, and stir 3 minutes (9,000 turn) to prepare the microfiber slurry of 1% concentration with the hydrabeating machine of 2 liters of 3000rpm 3/4 horsepower of Hermann Manufacturing Company manufacture.The operation described in preceding embodiment 20 is used to prepare handsheet.

Being separated and being formed of the optics of these handsheets and scanning electronic microscope observation display polyester microfiber is very good.

Claims

1., containing the composition of microfiber, comprise:

The mixture of sulfopolyester dispersion and multiple nonaqueous dispersion synthetic polymer microfiber,

Wherein said microfiber has the equivalent diameter being less than 5 microns and the length being less than 25 millimeters,

Wherein said sulfopolyester dispersion comprises at least one sulfonic polyester and water,

Wherein said at least one sulfonic polyester comprises:

(i) with the total amount of sour residue, the residue of one or more dicarboxylic acids of about 50 to about 96%, one or more dicarboxylic acids wherein said comprise terephthalic acid (TPA) and M-phthalic acid;

(iii) one or more diol residue,

Wherein said sulfonic polyester has the glass transition temperature of at least 40 DEG C,

Wherein said sulfonic polyester has the inherent viscosity of at least 0.2dL/g recorded with the concentration of 0.5 gram of sulfonic polyester/100mL solvent in 40 DEG C of 60/40 parts by weight solution in phenol/tetrachloroethane solvent,

Wherein said sulfonic polyester demonstrates the melt viscosity being less than 10000 pools recorded with the strain rate of 1 rad/sec at 240 DEG C.

2. the composition containing microfiber of claim 1, the wherein said composition containing microfiber is made up of described sulfopolyester dispersion and described microfiber substantially.

3. claim 1 containing the composition of microfiber, wherein said microfiber and sulfonic polyester are derived to be had described microfiber as its nonaqueous dispersion component and has the multicomponent fibre of described sulfonic polyester as its water dispersible compositions.

4. the composition containing microfiber of claim 1, the glass transition temperature that wherein said sulfonic polyester has at least 50 DEG C and the melt viscosity being less than about 6000 pools recorded with the strain rate of 1 rad/sec at 240 DEG C.

5. the composition containing microfiber of claim 1, wherein with the total amount of sour residue, described sulfonic polyester comprises the residue of one or more dicarboxylic acids described in about 80 to about 96 % by mole.

6. the composition containing microfiber of claim 1, wherein with the total amount of sour residue, described sulfonic polyester comprises the residue of the described at least one sulfomonomer of about 4 to about 20 % by mole.

7. the composition containing microfiber of claim 1, wherein said microfiber has the equivalent diameter being less than 3 microns.

8. the composition containing microfiber of claim 1, wherein said microfiber has the length being less than 3.5 millimeters.

9. the composition containing microfiber of claim 1, wherein said microfiber is made by being selected from following nonaqueous dispersion material: polyolefin, polyester, polyamide, polyactide, polycaprolactone, Merlon, polyurethane, cellulose esters, polyvinyl chloride and their mixture.

10., for the preparation of the technique of nonwoven articles, described technique is included in wet laid nonwoven technique the described composition containing microfiber using claim 1.

The technique of 11. claims 10, wherein uses the described composition containing microfiber to comprise and to be mixed with water by the described composition containing microfiber and obtained mixture is transferred to wet laid nonwoven district in described wet laying process.

The technique of 12. claims 10, wherein uses the described composition containing microfiber comprise the described composition containing microfiber and water and other fibers mixture and obtained mixture is transferred to wet laid nonwoven district in described wet laying process.

The 13. wet lapped compositions comprising water and multiple synthetic fiber, wherein said water accounts for the 50-90wt% of this wet lapped composition, wherein said synthetic fiber account for the 10-50wt% of this wet lapped composition, wherein said water and described synthetic fiber account at least 95wt% of this wet lapped composition altogether, wherein said synthetic fiber have the length being less than 25 millimeters and the smallest lateral dimension being less than 10 microns, and wherein said synthetic fiber are made up of nonaqueous dispersion synthetic polymer.

The wet lapped composition of 14. claims 13, wherein said synthetic fiber have the length being no more than 10 millimeters.

The wet lapped composition of 15. claims 13, comprising content is further at least 0.001wt% and be no more than the aqueous dispersion polymers of 5wt%.

The wet lapped composition of 16. claims 13, wherein said aqueous dispersion polymers comprises at least one sulfonic polyester;

Wherein sulfonic polyester described at least one have at least 40 DEG C glass transition temperature and 240 DEG C with the strain rate of 1 rad/sec record be less than about 10000 pool melt viscosities, wherein said at least one sulfonic polyester comprises:

(iii) one or more diol residue.

The wet lapped composition of 17. claims 13, wherein said nonaqueous dispersion synthetic polymer is selected from: polyolefin, polyester, copolyesters, polyamide, polyactide, polycaprolactone, Merlon, polyurethane, cellulose esters, acrylic polymer, polyvinyl chloride and their blend.

18. wet laying processes preparing nonwoven articles, described wet laying process comprises:

A () preparation comprises the multicomponent fibre of at least one water dispersible sulfonic polyester and one or more and the immiscible nonaqueous dispersion synthetic polymer of described sulfonic polyester, wherein said multicomponent fibre have be less than 15dpf be spun into denier;

C () makes described short multicomponent fibre of cutting contact with water to remove described sulfonic polyester, form the slurry of synthetic fiber in sulfopolyester dispersion thus, and wherein said sulfopolyester dispersion comprises water and described sulfonic polyester at least partially; And

D () removes described sulfopolyester dispersion at least partially from described slurry, prepare wet lapped composition thus, wherein said wet lapped composition comprises water and multiple described synthetic fiber, wherein said water accounts for the 50-90wt% of this wet lapped composition, wherein said synthetic fiber account for the 10-50wt% of this wet lapped composition, wherein said water and described synthetic fiber account at least 95wt% of this wet lapped composition altogether, and wherein said synthetic fiber have the length being less than 25 millimeters and the smallest lateral dimension being less than 5 microns.

The wet laying process of 19. claims 18, comprises further and described wet lapped composition is transferred to wet laid nonwoven district to prepare described nonwoven articles.

The wet laying process of 20. claims 18, comprises further and described wet lapped composition and other fiber being merged in described wet laid nonwoven district and/or in the upstream being close to described wet laid nonwoven district; Wherein said other fiber is selected from: cellulose fibre slurry, inorfil, polyester fiber, nylon fiber, Lyocell fibers, polyamide fiber, rayon fiber, cellulose ester fiber and their combination.