CA2427303A1 - Method for flexibilizing glass fiber nonwoven bound with cured ureaformaldehyde resin - Google Patents
Method for flexibilizing glass fiber nonwoven bound with cured ureaformaldehyde resin Download PDFInfo
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- CA2427303A1 CA2427303A1 CA 2427303 CA2427303A CA2427303A1 CA 2427303 A1 CA2427303 A1 CA 2427303A1 CA 2427303 CA2427303 CA 2427303 CA 2427303 A CA2427303 A CA 2427303A CA 2427303 A1 CA2427303 A1 CA 2427303A1
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- weight
- glass fiber
- water
- fiber nonwoven
- soluble polymer
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/34—Condensation polymers of aldehydes, e.g. with phenols, ureas, melamines, amides or amines
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/26—Polyamides; Polyimides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2369—Coating or impregnation improves elasticity, bendability, resiliency, flexibility, or shape retention of the fabric
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2926—Coated or impregnated inorganic fiber fabric
- Y10T442/2992—Coated or impregnated glass fiber fabric
Abstract
A method for flexibilizing a glass fiber nonwoven bound with a cured urea formaldehyde resin binder by admixing water, a cured urea formaldehyde resin, and a water-soluble polymer comprising a polymerized ethylenically unsaturated carboxylic acid monomer, the polymer having a weight average molecular weight of from about 65,000 to about 95,000; applying the aqueous admixture to a glass fiber nonwoven; and heating the admixture to at least about 120°C. Also disclosed are glass fiber nonwovens made using the method.
Description
CURED IJR.EA FORMALDEHYDE RESIN
BACK(~h,OUND OF THE INVENTION
This inventi~~n relates to a method for tlexibilizing cured urea formaldehyde resin-bound glass fiber nonwovens. 1'vlore :parkicularly, this invention relates to a method for flexibilizing a glass fiber nonwaven bound with a cured urea formaldehyde resin binder by admixing with water and a urea formaldehyde resin, a low molecular weight, water-soluble polymer ~;~~mprising a polymerized ethylenically unsaturated carboxylic acid io~ monomer; applying; the aqueous admixture to a glass tiber nonwoven; and heating the admixture to at least about L20'~C'. The invention also relates to a glass fiber nonwoven made using the metl'nod of the invention.
U.S. Patent 5,334,648 discloses acrylic, styrene-butadiene, and vinyl chloride copolymer latex modif ers for urea formaldehyde resins, the modifiers used at a level of about 10%, based on the weighs: of' the urea formaldehyde resin, in order to improve the wet and dry strength of a polymer-bound glass fiber mat.
U.S. Patent 5,804,254 discloses a method for flexibilizing a glass fiber nonwoven bound with a cured urea formaldehyde rosin binder in which the binder includes a cured urea formaldehyde resin and O.S-J°,% by weight, based on the weight of the urea 2c~ formaldehyde resin, of a water-soluble polymer comprising 40-1C10% by weight of a polymerized ethylenically unsaturated carboxylic: acid monomer, the polymer having a weight average molecular weight from 100,000 to 2,()00,000.
While the above methods can be used to tlexibilfze a glass fiber nonwoven bound with a cured urea. formaldehyde resin binder, there is a continuing need for improved methods that provide good strecxgth while being easier to apply as an aqueous admixture onto a glass fiber nonwoven. "Flexibilizing" herein is typically indicated by increased wet and dry strength and/or improved tear strength, relative to a glass fiber nonwoven not containing the water-soluble polymer herein.
3C~ BRIEF D1;?SC.'RIPTION OF 'THE INVENTION
In one aspoca of the present invention, there is provided a method for flexibilizing a glass fiber nonwovon bound with a cured urea formaldehyde resin binder comprising:
(a) admixing with water and a urea formaldehyde rosin, from about 0.5% to about 10% by weight, based crn the weight of the urea formaldehyde resin, of a water-soluble polytrter comprising from about 40% to about 100% by weight, based on polymer weight, of a polymrerized ethylenically unsaturated carboxylic acid monomer, s,~id polymer having a weight average molecular weight of from about 65,000 to about 95,000;
5~ (b) applying the aqueous adrni:xture of step a) t:o a glass fiber nonwoven;
and (c) heating the admixture to at least about 120"C.
In another aspect, the invention relates to a glass fiber nonwoven bound with a cured urea formaldehyde resin binder comprising from about 0.5'% to about 10%
by weight, based on the weight of the urea formaldehyde resin, of a water-soluble polymer 1o comprising from ;about 40% to about: 100% by weight, based on polymer weight, of a polymerized ethylenically unsaturated carboxylic acid monomer, said polymer having a weight average molecular weight of from about 6,000 to about 95,000.
The present invention provides a glass fiber nonwoven having good wet and dry tensile strength and tear strength. Moreover, aqueous admixtures comprising the water 1~~ soluble polymer ln:rein typically have low viscosity and are non-foaming.
Thus, the polymer can be used a higher levels (e.g., up to about 10°~'o by weight, based on the weight of the urea formaldehyde resign) without causing overall high viscosity that makes it difficult to use and handle the co~t~position on production equipment.
2o DETAILED DESCRIPTION OF THE INVENTION
Urea formaldehyde resins are well known and widely commercially available.
They are formed from the rcac;tion of urea and tW naldehyde to form compounds containing methylol groups, which subsequently under the application of heat, with or without catalysts, react further., or condense, or cure to form polymers. The methylol 2~~ groups in the resin are known tcy react with active hydrogen groups such as other methylol groups to form ether or meth~elen~e ~;roups thereby forming polymeric structures. Such polymeric structures are generally brittle and nowovens containing such resins as binders tend to be relatively inflexible. Examples of commercially available urea formaldehyde resins include Casc:o-Resin FG~~~487 and FG-515 (Borden, lnc.) and GP TM 2980 RESI
3o MATT"' Glass Mat Binder Resin.
The water-soluble polymer comprises from about 40% to about 100%, preferably from about 60% to about 100',%, by weight, based on polymer weight, of at least one polymerized ethyl~enically unsaturated carboxylic acid monomer. The water-soluble polymer is formed by the free radical addition polymerization of the ethylenically unsaturated monomers such as, for example, methacrylic acid, acrylic acid, crotonic acid, fumaric acid, malefic acid, 2-methyl malefic acid, itaconic acid, 2-methyl itaconic acid, a,b-methylene glutaric acid, and salts thereof. Alternatively, ethylenically unsaturated anhydrides that form carboxylic acids during or subsequent to polymerization may be used in the polymerization, such as, for example, malefic anhydride, itaconic anhydride, acrylic anhydride, and methacrylic anhydride.
Additional f;thylenically unsaturated monomers) may be copolymerized with the carboxylic acid monomer in an amount of from 0% to about 60%, preferably from 0% to about 40%, by weight, based on polymer weight, such as, for example, acrylic ester to monomers including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl metlnac:rylate, butyl methacrylate, isodecyl methacrylate, hydroxyethyl acr~ilate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate;
acrylamide or substituted acrylamides; styrene or substituted styrenes;
butadiene; vinyl acetate or other vinyl esters; aci°ylonitrile or methacrylonitrile; and the like. The optional, 1:~ additional ethyleni<;ally unsaturated monomer should be selected so as not to render the polymer insoluble in water. Thus, only lesser amounts of hydrophobic monomers may be used, while greater amount; <af hydrophilic monomers may be used, without compromising water solubility «f the polymer.
The water-soluble polymer preferably comprises a polymerized carboxylic acid 2o monomer selected from the group consisting of methacrylic acid, acrylic acid, and mixtures thereof. Tn one embodiment, the water-soluble polymer comprises acrylic acid copolymerized with acrylamide, vinyl acetate, or methyl acrylate, or mixtures thereof.
The water-soluble polymer may be prepared by solution polymerization in an aqueous medium ~by techniquca for polymerizing ethylenically-unsaturated monomers 2.5 which are well known in the art. By "aqueous" herein is meant that the medium is predominantly con-;posed of wader, although water-miscible organic solvents may also be present. The polymerization may be carried out by various means such as, for example, with all of the monomer in the reaction kettle at the beginning of the polymerization reaction or with some or all o I~ the monomer being added throughout the course of the 3~0 reaction.
The polymE;rization reaction to prepare the addition polymer may be initiated by various methods known in ~th~; art such as, for example, by using the thermal decomposition of an initiator and by using an oxidation-reduction reaction ("redox reaction") to generate free radicals to effect the polymerization.
The water-soluble polymer herein has a weight average molecular weight from about 65,000 to ah~out 05,000, preferably from about 70,000 to about 90,000, more preferably from about 70,000 to about 86,000, as measured by aqueous gel permeation chromatography. Molecular weights lower than about 65,Ot)0 may not provide the strength improvements desired. Molecul~~r weights higher than about 100,000 lead to a higher viscosity of the aqueous admi:~ture at a desirable solids level than is preferred for conventional meth<rds of appliczrtion to the glass fiber nonwoven. Chain transfer agents such as mercaptan,~, polymercaptans, and halogen compounds may be used in the polymerization mixvure in order' to moderate the molecular weight of the water-soluble.
to Generally, from 0°'° to about I°/a by weight, based.
on the weight of the polymeric binder, of C4-CZO alkyl men~aptans, merc:aptofrropionic acid, or esters of mercaptopropionic acid, may be used.
The aqueous admixture ma;y be prepared by admixing water, the urea formaldehyde resin. and from about 0.5°~° to about 10%, preferably from about 1% to ~5 about 7%, more pre-Ferably from about 1% to about 5%, by weight, based on the weight of the urea formaldeh~~de resin, of the water-soluble polymer using conventional mixing or stirring techniques to provide a laornogc.neous solution.
The aqueous admixture rnay contain, in addition, conventional adjuvants such as, for example, pigments, fillers, at7ti~-migration aids, curing agents, neutralizers, coalescents, 20 wetting agents, biocides, plasl:icizers, organosilanes, anti-foaming agents, colorants, waxes, and anti-oxi~;iants. The a queous admixture may also contain latex modifiers such as disclosed in U.~~. Patent 6,3a34~,llfi B1, incorporated herein by reference, to further flexibilize the glass tiber nonwo~~ens herein.
The aqueous admixture rnay be; applied to a glass fiber nonwoven by conventional 25 techniques such as, for example, air or airless spraying, padding, saturating, roll coating, curtain coating, be;~ter deposition, coagulation, and the like. The amount of aqueous admixture typically applied is from about 10~% to about 36°,'°, preferably from about 16%
to about 25%, LOI (Loss On Ignition), as determined using the following method.
The glass finer nonwovev may be prepared from fibers of' various lengths that may 3o have been previously subjected to various treatment or primer steps. The glass fiber nonwoven may be of various thi.cl<nesses as appropriate for the desired end use and may have been formed b:y wet laid or dry laid processes. The glass fiber nonwoven may contain heat-resistant fibers other than glass, i.e., fibers which are substantially unaffected by exposure to temperatures above about 120°C, such as, for example, aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyirnide fibers, certain polyester fibers, and rayon fibers. The nonwoven may also contain fibers that are not themselves heat resistant such as, for example, certain polyester tubers and nylon fibers, in so far as they do not adversely affect the performance of the nonwove:n.
The aqueous admixture, after it is applied to a glass fiber nonwoven, is heated to effect drying and curing. The clur;ation and temperature of heating will affect the rate of drying, processability, and handleability, and property development of the treated substrate. Heat treatment at ab~:>ut 120"C to about 400"C for a period of time between about 3 seconds to about 15 minutes may be carried out. 'treatment at about 150°C to 1C~ about 200°C is preferred. The e:lrying and curing functions may be conducted in two or more distinct steps., if desired. For example, the' composition may be first heated at a temperature and for a time sufficient to substantially dry but not to substantially cure the composition and then heated for a second time at a higher temperature and/or for a longer period of time to effect curing. "iuch a procedure, referred to as "B-staging", may be used 1 ~~ to provide binder-treated nonwoven, for example, in roll form, which may at a later stage be cured, with or without forming; or molding into a particular configuration, concurrent with the curing process.
The glass fiber nonwovens may be used for applications such as, for example, insulation bans or Trolls, as reinforcing mat for rooting or tlooring applications, as glass 2o mat based asphalt ;roofing shingles, as roving, as microglass-based substrate for printed circuit boards or battery separators, as filter stock, as tape stock, and as reinforcement scrim in cementitious and non-cementitious coatings for masonry.
TEST METHODS
25 Determination of weight average molecular weight:
Weight average moleci.~lar v~reight is determined by aqueous gel permeation chromatography on polyacid samples using a polyacrylic acid standard. Samples that are not 100% polycarboxylic acid are hydrolyzed to polyacid at l80°C for 60 hours in KOH/ethanol and tine molecular weight determined on the resulting polyacid, followed by 30 correction for the actual composition.
Determination of L~OI (Loss On Ignition):
A three-ind'n diameter piece of dried/cured fiberglass mat is cut using a circular die. The sample is weighed in a ceramic crucible and then placed in a muffle furnace at a temperature of 60()"C for 20 minutes. The sample is removed and then reweighed. % LOI
BACK(~h,OUND OF THE INVENTION
This inventi~~n relates to a method for tlexibilizing cured urea formaldehyde resin-bound glass fiber nonwovens. 1'vlore :parkicularly, this invention relates to a method for flexibilizing a glass fiber nonwaven bound with a cured urea formaldehyde resin binder by admixing with water and a urea formaldehyde resin, a low molecular weight, water-soluble polymer ~;~~mprising a polymerized ethylenically unsaturated carboxylic acid io~ monomer; applying; the aqueous admixture to a glass tiber nonwoven; and heating the admixture to at least about L20'~C'. The invention also relates to a glass fiber nonwoven made using the metl'nod of the invention.
U.S. Patent 5,334,648 discloses acrylic, styrene-butadiene, and vinyl chloride copolymer latex modif ers for urea formaldehyde resins, the modifiers used at a level of about 10%, based on the weighs: of' the urea formaldehyde resin, in order to improve the wet and dry strength of a polymer-bound glass fiber mat.
U.S. Patent 5,804,254 discloses a method for flexibilizing a glass fiber nonwoven bound with a cured urea formaldehyde rosin binder in which the binder includes a cured urea formaldehyde resin and O.S-J°,% by weight, based on the weight of the urea 2c~ formaldehyde resin, of a water-soluble polymer comprising 40-1C10% by weight of a polymerized ethylenically unsaturated carboxylic: acid monomer, the polymer having a weight average molecular weight from 100,000 to 2,()00,000.
While the above methods can be used to tlexibilfze a glass fiber nonwoven bound with a cured urea. formaldehyde resin binder, there is a continuing need for improved methods that provide good strecxgth while being easier to apply as an aqueous admixture onto a glass fiber nonwoven. "Flexibilizing" herein is typically indicated by increased wet and dry strength and/or improved tear strength, relative to a glass fiber nonwoven not containing the water-soluble polymer herein.
3C~ BRIEF D1;?SC.'RIPTION OF 'THE INVENTION
In one aspoca of the present invention, there is provided a method for flexibilizing a glass fiber nonwovon bound with a cured urea formaldehyde resin binder comprising:
(a) admixing with water and a urea formaldehyde rosin, from about 0.5% to about 10% by weight, based crn the weight of the urea formaldehyde resin, of a water-soluble polytrter comprising from about 40% to about 100% by weight, based on polymer weight, of a polymrerized ethylenically unsaturated carboxylic acid monomer, s,~id polymer having a weight average molecular weight of from about 65,000 to about 95,000;
5~ (b) applying the aqueous adrni:xture of step a) t:o a glass fiber nonwoven;
and (c) heating the admixture to at least about 120"C.
In another aspect, the invention relates to a glass fiber nonwoven bound with a cured urea formaldehyde resin binder comprising from about 0.5'% to about 10%
by weight, based on the weight of the urea formaldehyde resin, of a water-soluble polymer 1o comprising from ;about 40% to about: 100% by weight, based on polymer weight, of a polymerized ethylenically unsaturated carboxylic acid monomer, said polymer having a weight average molecular weight of from about 6,000 to about 95,000.
The present invention provides a glass fiber nonwoven having good wet and dry tensile strength and tear strength. Moreover, aqueous admixtures comprising the water 1~~ soluble polymer ln:rein typically have low viscosity and are non-foaming.
Thus, the polymer can be used a higher levels (e.g., up to about 10°~'o by weight, based on the weight of the urea formaldehyde resign) without causing overall high viscosity that makes it difficult to use and handle the co~t~position on production equipment.
2o DETAILED DESCRIPTION OF THE INVENTION
Urea formaldehyde resins are well known and widely commercially available.
They are formed from the rcac;tion of urea and tW naldehyde to form compounds containing methylol groups, which subsequently under the application of heat, with or without catalysts, react further., or condense, or cure to form polymers. The methylol 2~~ groups in the resin are known tcy react with active hydrogen groups such as other methylol groups to form ether or meth~elen~e ~;roups thereby forming polymeric structures. Such polymeric structures are generally brittle and nowovens containing such resins as binders tend to be relatively inflexible. Examples of commercially available urea formaldehyde resins include Casc:o-Resin FG~~~487 and FG-515 (Borden, lnc.) and GP TM 2980 RESI
3o MATT"' Glass Mat Binder Resin.
The water-soluble polymer comprises from about 40% to about 100%, preferably from about 60% to about 100',%, by weight, based on polymer weight, of at least one polymerized ethyl~enically unsaturated carboxylic acid monomer. The water-soluble polymer is formed by the free radical addition polymerization of the ethylenically unsaturated monomers such as, for example, methacrylic acid, acrylic acid, crotonic acid, fumaric acid, malefic acid, 2-methyl malefic acid, itaconic acid, 2-methyl itaconic acid, a,b-methylene glutaric acid, and salts thereof. Alternatively, ethylenically unsaturated anhydrides that form carboxylic acids during or subsequent to polymerization may be used in the polymerization, such as, for example, malefic anhydride, itaconic anhydride, acrylic anhydride, and methacrylic anhydride.
Additional f;thylenically unsaturated monomers) may be copolymerized with the carboxylic acid monomer in an amount of from 0% to about 60%, preferably from 0% to about 40%, by weight, based on polymer weight, such as, for example, acrylic ester to monomers including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl metlnac:rylate, butyl methacrylate, isodecyl methacrylate, hydroxyethyl acr~ilate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate;
acrylamide or substituted acrylamides; styrene or substituted styrenes;
butadiene; vinyl acetate or other vinyl esters; aci°ylonitrile or methacrylonitrile; and the like. The optional, 1:~ additional ethyleni<;ally unsaturated monomer should be selected so as not to render the polymer insoluble in water. Thus, only lesser amounts of hydrophobic monomers may be used, while greater amount; <af hydrophilic monomers may be used, without compromising water solubility «f the polymer.
The water-soluble polymer preferably comprises a polymerized carboxylic acid 2o monomer selected from the group consisting of methacrylic acid, acrylic acid, and mixtures thereof. Tn one embodiment, the water-soluble polymer comprises acrylic acid copolymerized with acrylamide, vinyl acetate, or methyl acrylate, or mixtures thereof.
The water-soluble polymer may be prepared by solution polymerization in an aqueous medium ~by techniquca for polymerizing ethylenically-unsaturated monomers 2.5 which are well known in the art. By "aqueous" herein is meant that the medium is predominantly con-;posed of wader, although water-miscible organic solvents may also be present. The polymerization may be carried out by various means such as, for example, with all of the monomer in the reaction kettle at the beginning of the polymerization reaction or with some or all o I~ the monomer being added throughout the course of the 3~0 reaction.
The polymE;rization reaction to prepare the addition polymer may be initiated by various methods known in ~th~; art such as, for example, by using the thermal decomposition of an initiator and by using an oxidation-reduction reaction ("redox reaction") to generate free radicals to effect the polymerization.
The water-soluble polymer herein has a weight average molecular weight from about 65,000 to ah~out 05,000, preferably from about 70,000 to about 90,000, more preferably from about 70,000 to about 86,000, as measured by aqueous gel permeation chromatography. Molecular weights lower than about 65,Ot)0 may not provide the strength improvements desired. Molecul~~r weights higher than about 100,000 lead to a higher viscosity of the aqueous admi:~ture at a desirable solids level than is preferred for conventional meth<rds of appliczrtion to the glass fiber nonwoven. Chain transfer agents such as mercaptan,~, polymercaptans, and halogen compounds may be used in the polymerization mixvure in order' to moderate the molecular weight of the water-soluble.
to Generally, from 0°'° to about I°/a by weight, based.
on the weight of the polymeric binder, of C4-CZO alkyl men~aptans, merc:aptofrropionic acid, or esters of mercaptopropionic acid, may be used.
The aqueous admixture ma;y be prepared by admixing water, the urea formaldehyde resin. and from about 0.5°~° to about 10%, preferably from about 1% to ~5 about 7%, more pre-Ferably from about 1% to about 5%, by weight, based on the weight of the urea formaldeh~~de resin, of the water-soluble polymer using conventional mixing or stirring techniques to provide a laornogc.neous solution.
The aqueous admixture rnay contain, in addition, conventional adjuvants such as, for example, pigments, fillers, at7ti~-migration aids, curing agents, neutralizers, coalescents, 20 wetting agents, biocides, plasl:icizers, organosilanes, anti-foaming agents, colorants, waxes, and anti-oxi~;iants. The a queous admixture may also contain latex modifiers such as disclosed in U.~~. Patent 6,3a34~,llfi B1, incorporated herein by reference, to further flexibilize the glass tiber nonwo~~ens herein.
The aqueous admixture rnay be; applied to a glass fiber nonwoven by conventional 25 techniques such as, for example, air or airless spraying, padding, saturating, roll coating, curtain coating, be;~ter deposition, coagulation, and the like. The amount of aqueous admixture typically applied is from about 10~% to about 36°,'°, preferably from about 16%
to about 25%, LOI (Loss On Ignition), as determined using the following method.
The glass finer nonwovev may be prepared from fibers of' various lengths that may 3o have been previously subjected to various treatment or primer steps. The glass fiber nonwoven may be of various thi.cl<nesses as appropriate for the desired end use and may have been formed b:y wet laid or dry laid processes. The glass fiber nonwoven may contain heat-resistant fibers other than glass, i.e., fibers which are substantially unaffected by exposure to temperatures above about 120°C, such as, for example, aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyirnide fibers, certain polyester fibers, and rayon fibers. The nonwoven may also contain fibers that are not themselves heat resistant such as, for example, certain polyester tubers and nylon fibers, in so far as they do not adversely affect the performance of the nonwove:n.
The aqueous admixture, after it is applied to a glass fiber nonwoven, is heated to effect drying and curing. The clur;ation and temperature of heating will affect the rate of drying, processability, and handleability, and property development of the treated substrate. Heat treatment at ab~:>ut 120"C to about 400"C for a period of time between about 3 seconds to about 15 minutes may be carried out. 'treatment at about 150°C to 1C~ about 200°C is preferred. The e:lrying and curing functions may be conducted in two or more distinct steps., if desired. For example, the' composition may be first heated at a temperature and for a time sufficient to substantially dry but not to substantially cure the composition and then heated for a second time at a higher temperature and/or for a longer period of time to effect curing. "iuch a procedure, referred to as "B-staging", may be used 1 ~~ to provide binder-treated nonwoven, for example, in roll form, which may at a later stage be cured, with or without forming; or molding into a particular configuration, concurrent with the curing process.
The glass fiber nonwovens may be used for applications such as, for example, insulation bans or Trolls, as reinforcing mat for rooting or tlooring applications, as glass 2o mat based asphalt ;roofing shingles, as roving, as microglass-based substrate for printed circuit boards or battery separators, as filter stock, as tape stock, and as reinforcement scrim in cementitious and non-cementitious coatings for masonry.
TEST METHODS
25 Determination of weight average molecular weight:
Weight average moleci.~lar v~reight is determined by aqueous gel permeation chromatography on polyacid samples using a polyacrylic acid standard. Samples that are not 100% polycarboxylic acid are hydrolyzed to polyacid at l80°C for 60 hours in KOH/ethanol and tine molecular weight determined on the resulting polyacid, followed by 30 correction for the actual composition.
Determination of L~OI (Loss On Ignition):
A three-ind'n diameter piece of dried/cured fiberglass mat is cut using a circular die. The sample is weighed in a ceramic crucible and then placed in a muffle furnace at a temperature of 60()"C for 20 minutes. The sample is removed and then reweighed. % LOI
is calculated using the equation: ~ioLOI =(weight befi~re burning-weight after burning) times 100/weight before burning.
The following examples illustrate some embodiments of this invention, but should not be construed to he any sort o f' limitation on its scope.
EXAMPLES
Example 1. Preparation of aqueous admixture of urea formaldehyde (UF) resin (FG-515 resin from Borden, l:nc.) and water- soluble polymer.
Admixtures are prepared at 25% solids content by mixing the following to components at ambient tempera~tu.re, 'with the pH adjusted to about 6-8 before mixing.
Quantities listed in 'fable l are ire grams.
TABL>=? 1 _ _,__ Resin Solids F
FG-515 55 ~15() 443.2450 443.2443.2406.8 .___ -.._ _. 3 ./_ ~' _1 _ _= 19.5 Polymer ~ c~45 Polymer 30 -- -- 8.3 -- -- --Polymer 34 -- -- -- l -- --3 8.75 Polymer 30 -- -- -- -- 21.25--Water -- 542.2 537.3541.7 538.1535.6 PD8168C2 48 ~
41.7 Latex Polymer 1 is a polyacrylic polymer comprising about 98% by weight acrylic acid and about 2% by ~~eight acrylainide having a weight average molecular weight of about 75,000 Polymer 2 is a polymer ccrmpnising about 34% acrylic acid, 33% acrylamide and 33% vinyl acetate, having a weight avE:rage molecular weight of about 67,500.
20~ Polymer 3 i<,~ a polymer ~::o~mprising about 49% acrylic acid, 49% vinyl acetate and 2% hydroxyethyl ac:rylate, having a weight average molecular weight of about 71,000.
Polymer 4 is a polymer comprising about 60% methyl acrylate and 40% acrylic acid, having a weight average ma~lw:.cul,ar weight of about 74,000.
PD8168C2 is an acrylic latex with a Tg of 85°C.
Example 2. Preparation of polyrner-bound glass fiber nonwovens.
Glass fiber nonwoven handsheets are prepared with Uwens Corning Fiberglas, Inc.
OCF 9501 1 inch (about 2.5 cm) length glass chop using approximately 6.25 grams of 5. glass fiber per sheet. The glass fiber is dispersed in water using about SOOmI of a 0.25%
solution of SuperFl~~c A130 (from Cytec) and about O.SmI Rhodameen VP-532 (from Rhodia, Inc.). Handsheets are f«n~ned in a Williarns handsheet mold. The wet sheets are transferred to a vacuum station and dewatered. The aqueous admixtures of Example 1 are applied, and excess is vacuumed oft: T'he sheets are dried/cured in a forced air oven at 200°C for 3 minutes. The binder amount on the sheets is about 24°/<. LOI.
The above glass fiber nonwoven sheets exhibit wet and dry tensile strength and tear strength superior to that obtained using the OF resin alone.
Various ear~bodiments ~~f this invention have been described. However, this disclosure should not be deemed to be a limitation on the scope of the invention.
1s Accordingly, various modifications, adaptations, and alternatives may occur to one skilled in the art without departing from: the spirit and scope of the claimed invention.
The following examples illustrate some embodiments of this invention, but should not be construed to he any sort o f' limitation on its scope.
EXAMPLES
Example 1. Preparation of aqueous admixture of urea formaldehyde (UF) resin (FG-515 resin from Borden, l:nc.) and water- soluble polymer.
Admixtures are prepared at 25% solids content by mixing the following to components at ambient tempera~tu.re, 'with the pH adjusted to about 6-8 before mixing.
Quantities listed in 'fable l are ire grams.
TABL>=? 1 _ _,__ Resin Solids F
FG-515 55 ~15() 443.2450 443.2443.2406.8 .___ -.._ _. 3 ./_ ~' _1 _ _= 19.5 Polymer ~ c~45 Polymer 30 -- -- 8.3 -- -- --Polymer 34 -- -- -- l -- --3 8.75 Polymer 30 -- -- -- -- 21.25--Water -- 542.2 537.3541.7 538.1535.6 PD8168C2 48 ~
41.7 Latex Polymer 1 is a polyacrylic polymer comprising about 98% by weight acrylic acid and about 2% by ~~eight acrylainide having a weight average molecular weight of about 75,000 Polymer 2 is a polymer ccrmpnising about 34% acrylic acid, 33% acrylamide and 33% vinyl acetate, having a weight avE:rage molecular weight of about 67,500.
20~ Polymer 3 i<,~ a polymer ~::o~mprising about 49% acrylic acid, 49% vinyl acetate and 2% hydroxyethyl ac:rylate, having a weight average molecular weight of about 71,000.
Polymer 4 is a polymer comprising about 60% methyl acrylate and 40% acrylic acid, having a weight average ma~lw:.cul,ar weight of about 74,000.
PD8168C2 is an acrylic latex with a Tg of 85°C.
Example 2. Preparation of polyrner-bound glass fiber nonwovens.
Glass fiber nonwoven handsheets are prepared with Uwens Corning Fiberglas, Inc.
OCF 9501 1 inch (about 2.5 cm) length glass chop using approximately 6.25 grams of 5. glass fiber per sheet. The glass fiber is dispersed in water using about SOOmI of a 0.25%
solution of SuperFl~~c A130 (from Cytec) and about O.SmI Rhodameen VP-532 (from Rhodia, Inc.). Handsheets are f«n~ned in a Williarns handsheet mold. The wet sheets are transferred to a vacuum station and dewatered. The aqueous admixtures of Example 1 are applied, and excess is vacuumed oft: T'he sheets are dried/cured in a forced air oven at 200°C for 3 minutes. The binder amount on the sheets is about 24°/<. LOI.
The above glass fiber nonwoven sheets exhibit wet and dry tensile strength and tear strength superior to that obtained using the OF resin alone.
Various ear~bodiments ~~f this invention have been described. However, this disclosure should not be deemed to be a limitation on the scope of the invention.
1s Accordingly, various modifications, adaptations, and alternatives may occur to one skilled in the art without departing from: the spirit and scope of the claimed invention.
Claims (20)
1. A method for flexibilizing a glass fiber nonwoven bound with a cured urea formaldehyde resin binder, comprising:
a) admixing with water and a urea formaldehyde resin, from about 0.5% to about 10% by weight, based on the weight of the urea formaldehyde resin, of a water-soluble polymer comprising from about 40% to about 100% by weight, based on polymer weight, of a polymerized ethylenically unsaturated carboxylic acid monomer, said polymer having a weight average molecular weight of from about 65,000 to about 95,000;
b) applying; the aqueous admixture of step a) to a glass fiber nonwoven; and c) heating the admixture; to at least about 120°C.
a) admixing with water and a urea formaldehyde resin, from about 0.5% to about 10% by weight, based on the weight of the urea formaldehyde resin, of a water-soluble polymer comprising from about 40% to about 100% by weight, based on polymer weight, of a polymerized ethylenically unsaturated carboxylic acid monomer, said polymer having a weight average molecular weight of from about 65,000 to about 95,000;
b) applying; the aqueous admixture of step a) to a glass fiber nonwoven; and c) heating the admixture; to at least about 120°C.
2. The method of claim 1 wherein the water-soluble polymer comprises a polymerized carboxylic acid monomer selected from the group consisting of methacrylic acid, acrylic acid, and mixtures thereof.
3. The method of claim 2 wherein the water-soluble polymer comprises acrylic acid copolymerized with acrylamide, vinyl acetate, or methyl acrylate, or mixtures thereof.
4. The method of claim 2 wherein the water-soluble polymer has a weight average molecular weight of from about 70,000 to about 90,000.
5. The method of claim 4 wherein the water-soluble polymer has a weight average molecular weight of from about 70,000 to about 85,000.
6. The method of claim 5 comprising admixing from about 1% to about 5% by weight of the water-soluble polymer in step a).
7. The method of claim 1 wherein the water-soluble polymer has a weight average molecular weight of from about 70,00 to about 90,000.
8 8. The method of claim 7 comprising admixing from about 1% to about 5% by weight of the water-soluble polymer in step a).
9. The method of claim 1 wherein the amount of aqueous admixture applied to the glass fiber nonwoven is from about 10% to about 35% LOI.
10. The method of claim 6 wherein the amount of aqueous admixture applied to the glass fiber nonwoven is from about 15% to about 25% LOI.
11. A glass fiber nonwoven bound with a cured urea formaldehyde resin binder comprising from about 0.5% to about 10% by weight, based on the weight of the urea formaldehyde resin, of a water-soluble polymer comprising from about 40%
to about 100% by weight, based on polymer weight, of a polymerized ethylenically unsaturated carboxylic acid monomer, said polymer having a weight average molecular weight of from about 65,000 to about 95,000.
to about 100% by weight, based on polymer weight, of a polymerized ethylenically unsaturated carboxylic acid monomer, said polymer having a weight average molecular weight of from about 65,000 to about 95,000.
12. The glass fiber nonwoven of claim 11 wherein the water-soluble polymer comprises a polymerized carboxylic acid monomer selected from the group consisting of methacrylic acid, acrylic acid, and mixtures thereof.
13. The glass fiber nonwoven of claim 12 wherein the water-soluble polymer comprises acrylic acid copolymerized with acrylamide, vinyl acetate, or methyl acrylate, or mixtures thereof.
14. The glass fiber nonwoven of claim 12 wherein the water-soluble polymer has a weight average molecular weight of from about 70,000 to about 90,000.
15. The glass fiber nonwoven of claim 14 wherein the water-soluble polymer has a weight average molecular weight of from about 70,000 to about 85,000.
16. The glass fiber nonwoven of claim 15 comprising from about 1% to about 5%
by weight, based on the weight of the urea formaldehyde resin, of the water-soluble polymer.
by weight, based on the weight of the urea formaldehyde resin, of the water-soluble polymer.
17. The glass filer nonwoven of claim 11 wherein the water-soluble polymer has a weight average molecular weight of from about 70,000 to about 90,000.
18. The glass fiber nonwoven of claim 17 comprising from about 1% to about 5%
by weight, based on the weight of the urea formaldehyde resin, of the water-soluble polymer.
by weight, based on the weight of the urea formaldehyde resin, of the water-soluble polymer.
19. The glass fiber nonwoven of claim 11 wherein the urea formaldehyde resin binder is applied to the glass fiber nonwoven in the form of an aqueous admixture in an amount of from about 10% to about 35% LOI.
20. The glass fiber nonwoven of claim 16 wherein the urea formaldehyde resin binder is applied to the glass fiber nonwoven in the form of an aqueous admixture in an amount of from about 10% to about 35% LOI.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/427,241 US20040219847A1 (en) | 2003-04-30 | 2003-04-30 | Method for flexibilizing glass fiber nonwoven bound with cured urea formaldehyde resin |
| US10/427,241 | 2003-04-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2427303A1 true CA2427303A1 (en) | 2004-10-30 |
Family
ID=33310085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2427303 Abandoned CA2427303A1 (en) | 2003-04-30 | 2003-04-30 | Method for flexibilizing glass fiber nonwoven bound with cured ureaformaldehyde resin |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US20040219847A1 (en) |
| CA (1) | CA2427303A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7625828B2 (en) * | 2004-01-08 | 2009-12-01 | Certainteed Corporation | Insulation product having nonwoven facing |
| US7544267B2 (en) * | 2004-01-08 | 2009-06-09 | Certainteed Corporation | Method of making insulation product having nonwoven facing |
| CA2863990C (en) | 2013-09-30 | 2021-04-13 | Rohm And Haas Company | Methacrylic acid polymer extended urea-formaldehyde resin compositions for making fiberglass products |
| US11214919B2 (en) * | 2018-05-31 | 2022-01-04 | Ecolab Usa Inc. | Wet web strength for fiberglass mats |
| KR20210151883A (en) * | 2019-04-09 | 2021-12-14 | 오웬스 코닝 인텔렉츄얼 캐피탈 엘엘씨 | aqueous binder composition |
| US11813833B2 (en) | 2019-12-09 | 2023-11-14 | Owens Corning Intellectual Capital, Llc | Fiberglass insulation product |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5334648A (en) * | 1991-10-30 | 1994-08-02 | The B. F. Goodrich Company | Emulsion polymers for use as a urea formaldehyde resin modifier |
| US5661213A (en) * | 1992-08-06 | 1997-08-26 | Rohm And Haas Company | Curable aqueous composition and use as fiberglass nonwoven binder |
| US5804254A (en) * | 1996-09-07 | 1998-09-08 | Rohm And Haas Company | Method for flexibilizing cured urea formaldehyde resin-bound glass fiber nonwovens |
| US5846603A (en) * | 1997-07-28 | 1998-12-08 | Superior Fibers, Inc. | Uniformly tacky filter media |
| US6993876B1 (en) * | 2000-01-18 | 2006-02-07 | Building Materials Investment Corporation | Asphalt roofing composite including adhesion modifier-treated glass fiber mat |
| US6384116B1 (en) * | 2000-01-25 | 2002-05-07 | Borden Chemical, Inc. | Binder composition and process |
-
2003
- 2003-04-30 US US10/427,241 patent/US20040219847A1/en not_active Abandoned
- 2003-04-30 CA CA 2427303 patent/CA2427303A1/en not_active Abandoned
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