CA2145470A1 - Abrasion-resistant polyester mixture with enhanced consistency of processing, monofilaments therefrom, and production and use thereof - Google Patents
Abrasion-resistant polyester mixture with enhanced consistency of processing, monofilaments therefrom, and production and use thereofInfo
- Publication number
- CA2145470A1 CA2145470A1 CA002145470A CA2145470A CA2145470A1 CA 2145470 A1 CA2145470 A1 CA 2145470A1 CA 002145470 A CA002145470 A CA 002145470A CA 2145470 A CA2145470 A CA 2145470A CA 2145470 A1 CA2145470 A1 CA 2145470A1
- Authority
- CA
- Canada
- Prior art keywords
- abrasion
- carbon atoms
- polyester
- mixture
- resistant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F1/00—Wet end of machines for making continuous webs of paper
- D21F1/0027—Screen-cloths
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2964—Artificial fiber or filament
- Y10T428/2967—Synthetic resin or polymer
- Y10T428/2969—Polyamide, polyimide or polyester
Abstract
Abrasion-resistant polyester mixture with enhanced consistency of processing, monofilaments therefrom, and production and use thereof Described is an abrasion-resistant polyester mixture with enhanced consistency of processing, comprising a thermoplastic polyester and a thermoplastic polyurethane with or without customary nonpolymeric additives, the mixture of said polyester and said polyurethane having a melting point between 200 and 230°C, as are monofilaments made of said mixture.
Also described are the production of this abrasion-resistant polyester mixture, the production of monofila-ments therefrom, and their use for producing paper machine wire cloths.
Also described are the production of this abrasion-resistant polyester mixture, the production of monofila-ments therefrom, and their use for producing paper machine wire cloths.
Description
214~70 HOECHST A~L~ SELLSCHAFT HOE 94/F 079 Dr.VA/
Abrasion-resistant polyester mixture with ~nh~nced consistency of processing, monofilaments therefrom, and production and use thereof The present invention relates to an abrasion-resistant polyester mixture with enh~nced consistency of proces-sing, to monofilaments spun therefrom, which can be used with particular advantage for producing paper machine wire cloths, and to the production and use thereo$.
Synthetic fibers and fil ments and also sheetlike materials therefrom, such as woven or knitted fabrics, which are to be used for technical applications are generally exposed to far higher stresses than fiber materials for purely textile applications, for example in the clothing sector.
A very typical application for technical fiber materials is the production of paper machine wire cloths. Paper machine wire cloths are exposed in use to a ben~;ng and stretching stress, constant flection, high temperatures in a moist environment and a high abrasive stress.
Even in these mechanical and chemical stresses, paper machine wire cloths must keep their strength, dimensional stability and planarity for as long as possible; that is, they may also only show minimal swelling due to water absorption.
It is especially the abrasive stress, due on the under-side to rubbing of the wire cloths against support elements of the paper machine and against sealing elements above the suction boxes, where the paper web is drained, and on the inside of the wire cloths to rubbing of the filaments against each other and to the flow-through of water cont~;n;ng abrasive paper filler, which has a very great effect on wire cloth life.
It has proved to be extremely difficult to provide a wire cloth material which is sufficiently resistant to all the stresses mentioned.
2145~70 The original Fourdrinier papermaking machine wire cloths were in fact made of metal wires, the metal used being phosphorus bronze.
Although these metal wires are very resistant to the high temperatures and the hydrolytic attack, they have unsatisfactory abrasion characteristics. It has also already been proposed to make paper machine wire cloth~
from polyester filaments, especially polyethylene or polybutylene terephthalate filaments, or from polyamide filaments, for example nylon-6 or nylon-6,6 filaments.
It is true that polyester filaments possess good dynamic stability and, because of their low moisture regain, good dimensional stability, but their chemical resistance at high temperatures generally leaves something to be desired, and their abrasion resistance in particular does not meet the requirements of papermaking machine manufacturers.
Polyamide filaments, by contrast, do show good abrasion resistance, but have a high moisture regain coupled with high swelling and low dimensional stability.
Various publications, for example US-A-4 529 013, US-A-4 289 173 and DE-A-2 502 466, have already described attempts to combine polyester and polyamide filaments to produce paper machine wire cloths which are better equipped to meet the high requirements.
However, these attempts have only been partially suc-cessful; more particularly, new difficulties arise as a result of using different filament materials in one and the same fabric.
Another way was proposed in EP-A-0 387 395, which recom-mends weaving paper machine wire cloths from polyester filaments, especially polyethylene terephthalate fila-ments, using a weft consisting at least partly of filaments of a polyester cont~;ning 10 to 40% by weight of a thermoplastic urethane and up to 5% by weight of a hydrolysis stabilizer.
A similar proposal is known from DE-T-3 249 110, which recommends producing filaments for paper machine wire cloths from a mixture of a polyester, a polyester stabilizer and a "thermoplastic material", wherein the "thermoplastic material" used is said to be a thermo-plastic polyurethane or a polyether-ester block copolymer.
It is stated in both documents that these polyester mixtures result in filaments of improved hydrolysiR
resistance and improved abrasion resistance.
However, a serious disadvantage of these known polyester mixtures is that melt sp; nn; ng these mixtures gives rise to the formation, in the melt, of gas bubbles which reduce the consistency of processing. This evolution of gas is presumably due to the onset of the decomposition of the polyurethane component.
It has now been found that it is possible to produce polyester mixtures which are processible, especially spinnable, without noticeable gas evolution and which are spinnable into the filaments which combine the good mechanical properties of polyester with appreciably improved abrasion characteristics.
The present invention accordingly provides an abrasion-resistant polyester mixture with onh~nced consistency of processing, comprising a thermoplastic polyester and a thermoplastic polyurethane with or without customary nonpolymeric additives, the mixture of said polyester and said polyurethane having a melting point be_ween 200 and 230C.
The polymer material of the abrasion-resistant polyester mixture of the present invention contains from 60 to 95% by weight, preferably from 70 to 90% by weight, of said thermoplastic polyester and from 5 to 40% by weight, preferably from 10 to 30% by weight, of said thermoplastic polyurethane.
The thermoplastic polyester of the abrasion-resistant polyester mixture of the present invention has a glass 2145~70 transition point of 68 to 82C, preferably 72 to 80C, a crystallization point of 135 to 155C, preferably 140 to 150C, and a melting point within the range from 175C to 235C.
The melting point range of the abrasion-resistant poly-ester mixture of the present invention and the tem-perature ranges of the glass transition point, of the crystallization point and of the melting point of the thermoplastic polyester present in the abrasion-resistant polyester mixture of the present invention are based on a measurement in a differential sc~nn;ng calorimeter (DSC) at a temperature rise rate of 10C per minute.
The polyester of the abrasion-resistant polyester mixture of the present invention preferably has a melt viscosity of 445 to 482 Pa.s, preferably 455 to 475 Pa.s, especi-ally of 460 to 468 Pa.s, when measured at 245 + 2C and a shear gradient of 200 + 5 8-1, and of 245 to 282 Pa.s, preferably 250 to 272, especially of 255 to 270 Pa.s when measured at the same temperature and a shear gradient of 1,200 + 5 8-1 .
The thermoplastic polyesters of the abrasion-resistant polyester mixture of the present invention consist pre-~;n~ntly, i.e. at least 70 mol%, based on the totality of all polyester units, of common units derived from aromatic dicarboxylic acids and from aliphatic diols.
Common aromatic dicarboxylic acid unit~ are derived from benzenedicarboxylic acids, especially terephthalic acid and isophthalic acid; common diols have 2-4 carbon atoms, and ethylene glycol is particularly ~uitable.
The remaining 30 mol%, based on the totality of all polyester units, are then made up of dicarboxylic acid units and diol units which differ from the aromatic units forming the predominant portion of the units and which act as modifiers and make it possible for the person skilled in the art to influence the physical and chemical properties of the filaments in a specific manner.
21~47~
Examples of such dicarboxylic acid units are radicals of aromatic dicarboxylic acids differing from the aromatic dicarboxylic acid units forming the pre~om;nAnt portion of the dicarboxylic acid units, or radical~ of arali-phatic dicarboxylic acids having one or more, preferablyone or two, fused or unfused aromatic nuclei, for example of isophthalic acid, 5-sulfoisophthalic acid, 5-sulfopro-poxyisophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, p-phenylenediacetic acid, 4,4'-oxydiphenyldicarboxylic acid or diphenoxyalkanedi-carboxylic acid, or radicals of cyclic or acyclic aliphatic dicarboxylic acids, for example trans-hexa-hydroterephthalic acid, 1,2-cyclobutane~;carboxylic acid, glutaric acid, adipic acid, sebacic acid; examples of modifying diol radicals are those of branrhe~ and/or long-chain diols having 3 to 10, preferably 3 to 6, carbon atoms, for example of 1,3-propanediol, 1,4-butanediol, 1,6-h~Yane~;ol, 2,2-dimethylpropanediol or 2-ethyl-1,6-hexanediol, or of cyclic diols, for example of 1,4-hydroxymethylcyclohexane, or of diols that contain ether groups, for example of diethylene or triethylene glycol, or, if present in a small a_ount, of polyglycol having a molecular weight of about 500-2,000.
Particular preference for use as constituents of the abrasion-reQistant polye~ter mixture of the present invention is given to those thermoplastic polyesters whose polymer rha;n~, based on the totality of all polyester units, is composed of 35 to 47 mol% of units of the formula -C0-Al-C0- (I) 3 to 15 mol% of units of the formula -C0-A2-C0- (II) 35 to 50 mol% of units of the formula -0-Dl-0- (III) 0 to 15 mol% of units of the formula -o-D2-0- (IV) where A1 denotes aromatic radicals having 5 to 12, preferably 6 to 10, carbon atoms, A2 denotes aromatic radicals differing from Al or arali-phatic radicals having 5 to 16, preferably 6 to 12, 21~5~70 carbon atoms or cyclic or acyclic aliphatic radicals having 2 to 10 carbon atoms, preferably 4 to 8 carbon atoms, Dl denotes alkylene or polymethylene groups having 2 to 4 carbon atoms or cycloalkane or dimethylenecycloalkane groups having 6 to 10 carbon atoms, D2 denotes non-D~ alkylene or polymethylene groups having 3 or 4 carbon atoms or cycloalkane or dimethylenecycloalkane groups having 6 to 10 carbon atoms or straight chain or branched alkanediyl groups having 4 to 16, preferably 4 to 8, carbon atoms or radicals of the formula -(C2H4-O)m-C2H4-, where n is an integer from 1 to 40, with m = 1 or 2 being preferred for proportions of up to 20 mol% and groups with m = 10 to 40 preferably being present only in proportions of below 5 mol%.
The polyesters present in the polyester mixture of the present invention have a relative viscosity of advan-tageously 1.6 to 2.2, preferably 1.8 to 2.0, measured in a 1% strength by weight solution of the polyesters in dichloroacetic acid at 25C.
Preferred aryl Al is 1,4-phenylene, preferred aryl A2 is in particular 1,3-phenylene or else 1,4-, 1,5-, 1,8-, 2,6- and 2,7-naphthylene, 4,4'-biphenylene, furylene or a radical of the formula VI
~Z ~ ~1) where Z is polymethylene or alkylene of 1 to 4 carbon atoms, -SO2-, -C00-, -0- or -S-.
Radicals denoted by Al and A2 can all be identical within the scope of the definition given, or they can be different.
More particularly, the abovementioned radicals represen-ted by Al can be present in the polyester chain indi-vidually or mixed. It is preferable for Al to be formed 21~470 by only one or two members of the group of radicals specified for A1. Any desired further modification of the polyester chain is then preferably effected through other units within the scope of the definition for A2.
For instance, the aromatic radicals A1 can all be 1,4-phenylene radicals or they can be composed for example in a molar ratio of 4:6 to 6:4 of 2,6-naphthylene radicals and 4,4'-biphenyldiyl radicals.
Preference iB given to polyesters in which A1 i~
1,4-phenylene and especially to those in which A2 is likewise aryl.
Similarly, the radicals denoted by D1 and D2 can all be identical within the scope of the definition given, or they can be different.
More particularly, the abovementioned radicals represen-ted by D1 can be present in the polyester chain indi-vidually or mixed. It is preferable for D1 to be formed by only one or two members of the group of radicals specified for D1. Any desired further modification of the polyester chain is then preferably effected through other units within the scope of the definition for D2.
For instance, the radicals D1 can all be ethylene radi-cals or they can be composed for example in a molar ratio of lO:1 to 1:10 of ethylene-1,4-dimethylenecyclo~eYAne radicals.
Particular preference is given to polyesters in which is exclusively ethylene.
Particular preference is further gi~en to polyesters in which A1 is 1,4-phenylene and A2 is 1,3-phenylene.
Particular preference is further given to polyesters with 40 to 47 mol% of units of the formula I, 3 to 10 mol% of units of the formula II, 48 to 50 mol%, especially 50 mol%, of units of the formula III and 0 to 2, especi-ally 0, mol% of units of the formula IV.
The nuclei of the aromatic and araliphatic radicals represented by A1 and A2 may in turn additionally carry one or two substituents. In this case, however, it is preferable for only a proportion of up to 15%, especially up to 7%, of the aromatic radicals present to be substi-tuted. Preferably, the substituted aromatic radicals eachcarry only one substituent. Particularly suitable sub-stituents are alkyl having 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and sulfo.
Radicals derived from aliphatic dicarboxylic acids and aromatic radicals which yield angled chA;nR, for example isophthalic radicals, or which comprise rather bulky aromatic nuclei, such as the naphthalene nucleus, and also the long-chain groups Y are incorporated in parti-cular into the polyester chain when a further modifi-cation of the properties of the polyester is desired.
Preference is given to polyesters which contain less than7% of these modifying components.
The thermoplastic polyurethane present in the abrasion-resistant polyester mixture of the present invention is primarily characterized by application-specific physical properties.
It preferably has a shear modulus of 8 to 80 MPa, prefer-ably 20 to 50 MPa, within the temperature range from 20 to 60C, a mechanical 1088 factor tan(~) of 0.8*10-2 to 1.2*10-within the temperature range from 20 to 60C, a Shore A hardness, measured in accordance with DIN 53505, of 82 to 100, and a Shore D hardness, measured in accordance with DIN 53505, of 30 to 60.
It is further preferable for the thermoplastic polyurethane of the abrasion-resistant polyester mixture of the present .nvention to have a tensile strength, measured in accordance with DIN 53504, of 32 to 42 MPa, a breA~;ng extension, measured in accordance with DIN 53504, of 420 to 520% and an impact toughnes6, measured in accordance with DIN 53515 of 32 to 45%.
214517~
-g The thermoplastic polyurethane of the abrasion-re~istant polyester mixture of the present invention conforms to the idealized formula V
--O-CO-NH-R1-NH-CO-O-R2 (v) -n where Rl is a bivalent, aromatic or aralipha~ic radical of 6 to 18 carbon atoms with a substituted or unsubstituted aromatic ring or with two fused or unfused, substituted or unsubstituted aromatic rings, R2 is a polyether unit of the formula VI
O- CH2- CH O-- (Vl) -m where X3 is hydrogen or methyl, and m is from 10 to 100, preferably from 10 to 30, or the radical of polytetra-hydrofuran or preferably a polyester unit of the formula VII
~ _ _ --o-R3-o-Co-R4-Co ~R3~_ -p- -r (Vll) where R3 is straight-chain or optionally branched alkane-diyl or oxaalkanediyl having 2 to 8, preferably 2 to 6, carbon atoms, for example ethylene, 1,3-propanediyl, 1,4-but~ne~;yl, 1,6-hexanediyl, 2-ethyl-1,6-hexanediyl, 2,2-dimethyl-1,3-propanediyl, or the bivalent ox~ ne-diyl radicals derived from diethylene glycol or triethy-lene glycol, R4 iB alkanediyl having 2 to 6, preferably 2 to 4, carbon atoms, cycloalkanediyl such as 1,4- or 1,3-cyclohexane-diyl or a bivalent aromatic radical ha~ing 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, especially 1,3-or 1,4-phenylene, p i~ a number 80 that R4 has a molecular weight of 1,000 to 2,000 (p = 5 to 12, preferably 8 to 11) and q is either 0 or 1.
The polyurethane present in the abrasion-resistant polyester mixture of the present invention was said above to conform to an n idealized~ formula. This means that the formula does not strictly reflect the real structure of the polyurethane. Polyurethanes, as is be known, are produced by reacting diisocyanates with hydroxyl-cont~;n;ng polyethers or polyesters. The high reactivityof the diisocyanates, howe~er, may also gi~e rise, to a minor extent, to secondary reactions which lead to products whose structure is not described by the indi-cated formula.
Nevertheless, the idealized formula is, to the person skilled in the art, a completely adequate description of the polyurethane used, since it reveals which starting materials were combined to form the product in question.
The person skilled in the art is thus enabled by the formula to prepare the thermoplastic polyurethane present in the abrasion-resistant polyester mixture of the present invention.
The abrasion-resistant polyester mixture of the present invention preferably comprises a thermoplastic poly-urethane of the idealized formula V where R1 is pheny-lene, naphthalene or a unit of the formulae VIII or IX
~X1- ~3X2~
Vlll IX
which may each carry substituents, where Xl is a bivalent aliphatic radical having 1 to 3 carbon atoms and x2 is a direct bond, a bivalent aliphatic radical having 1 to 3 carbon atoms, -CO-, -SO2-or -NH-CO-NH-.
Particular preference is given to those abrasion-resistant polyester mixtures of the present invention which comprise a thermoplastic polyurethane of the idealized formula V
where Rl i8 a unit of the formula X
~CH2~ ~
The aromatic rings present in the thermoplastic polyurethane may be unsubstituted or carry one or two substituents selected from the group consisting of -SO3H
and -CH3.
Some thermoplastic polyurethanes having the above-indicated features are commercially available.
A polyurethane which i8 very suitable for use aR a constituent of the abrasion-resistant polyester mixture of the present invention is for example ~DESMOPAN VPRA 8392 from-BAYER AG.
The abrasion-resistant polyester mixture ol the present invention may comprise up to 10% by weight of non-polymeric substances, such as modifiers, fillers, pig-ments, dyes, antioxidants, hydrolysis, light and temperature stabilizers and/or processing aids.
Particularly preferred abrasion-resistant polyester mixtures of the present invention comprise in particular up to 10% by weight, preferably up to 5% by weight, of polyester stabilizers which protect the polyester in the mixture against hydrolysiE and thermal degradation.
Of particular advantage for use as stabilizers are those compounds capable of reacting with the ter~; n~ 1 carboxyl groups of the polyester to form nonacid end groups, for example glycidyl ethers, keteneimines, aziridines, iso-cyanates. Of particular advantage for use as stabilizers are carbodiimides and polycarbodiimides, especially if used combined with one another.
The abrasion-resistant polyester mixtures of the present invention are homogeneous mixtures of the mixture com-ponents. "Homogeneous" for the purposes of this inven-tion, however, is not restricted to solution-like, i.e.
molecularly diRperse, distributions, but the mixture may also consist of a uniform mixture of the pulverulent ingredients or of a uniform mixture of pellets or chips of the mixture constituents.
What matters is merely that the mixtures can be melted in an extruder to form a melt which retains the same com-position during extrusion, thus always producing an extrudate of unambiguously defined composition.
In the case of abrasion-resistant polyester mixtures of the present invention which consist of a homogeneous mixture of powders or even larger particles, for example pellets, any nonpolymeric constituents of the abrasion-resistant polyester mixture of the present invention willgenerally be located in the particles of the polyester and/or of the polyurethane, preferably in the polyester particles.
The abrasion-resistant polyester mixture of the present invention is produced by mixing the above-described thermoplastic polyesters and polyurethanes in suitable known mixing apparatus, for example mixing drums or 211547~
kneaders. These polymeric constituents can be present in solid form, for example as powders, chips or pellets, or as melts. It is of course also possible to stir a pulverulent ingredient into a melt of the other. The choice of mixing apparatus is made on the basis of suitability for the job in hand; that is, the chosen mixing apparatus must be adapted to the physical state of the ingredients to be mixed.
If the ingredients melt in the course of being mixed, which given thorough ~;Y;ng of the melt leads to particu-larly good or even molecularly disperse homogenization of the abrasion-re~istant polyester mixture of the present invention, extrusion and pelletization of the melt can be used to obtain the abrasion-resistant polyester mixture of the present invention in the form of uniform pellets or chips.
Nonpolymeric ingredients are generally incorporated into one or both of the polymer components, preferably into the polyester component.
A particularly advantageous embodiment of producing the abrasion-resistant polyester mixture of the present invention, comprises combining the polymer components, which may contain nonpolymeric ingredients already present, in the desired mixing ratio immediately upstream of the extruder inlet. Homogenization of the mixture is then effected in the feeding and mixing zone of the extruder screw. The material mixed and homogenized in the extruder can then be extruded directly to the desired articles, preferably the monofilaments of the present invention.
The present invention further provides monofilaments consisting of the above-described abrasion-resistant polyester mixture of the present invention.
These monofilaments have a linear density of 70 to 40,000 dtex, preferably 157 to 2,200 dtex, an initial modulus of 400 to 800, preferably 500 to 700, cN/tex, a tenacity of 15 to 30, preferably 20 to 30, cN/tex, a 21~5470 bre~king extension of 50 to 70%, preferably 60 to 65%, a 180C dry heat shrinkage of 10 to 40%, preferably 15 to 20%, with the development of a shrinkage tension of 0.1 to 0.5, preferably 0.2 to 0.3, cN/tex, and a boil off shrinkage of 3 to 10%, preferably 4 to 7%.
The monofilaments can be produced with different cross-~ectional shapes, including as hollow filaments. A round cross section is preferred.
These monofilaments can be used with particular ad~antage for the production of paper machine wire cloths.
To produce the monofilament~ of the pre~ent invention, the abrasion-resistant polyester mixture of the pre~ent invention i~ dried directly prior to sp;nn;ng, preferably by heating in a dry atmosphere or under reduced pre~sure.
Thereafter the abra~ion-resistant polyester mixture of the present invention is melted and homogenized in an extruder. Alternatively, as stated above, the thermo-plastic polyester and the polyurethane components of the abrasion-resistant polyester mixture of the present invention can also be separately predried and fed into the extruder in the de~ired mixing ratio.
The melt completely homogenized in the extruder i~
filtered in a customary spin pack and extruded through a ~pinneret at a melt temperature of 185 to 245C, prefer-ably 210 to 235C. The extruded molten filament is cooled in a spin bath (for example water at about 70C) and wound up or taken off at a speed which is greater than the extru~ion speed of the copolyester melt 80 that a drawdown of 1:2 to 1:4, preferably 1:2.5 to 1:3.5, results.
The extrusion speed is advantageously set in such a way that, in the interests of economical production of the monofilaments of the present invention, a sp;nn;ng take-off speed of 5 to 30, preferably 15 to 25, m per minute can be used.
2145~70 Of particular importance for the production of the mono-filaments of the present invention i8 the maintenance of the melt temperature range mentioned above. This tempera-ture ensures the production of filaments which are in accordance with the present invention and have optimum application properties. This temperature range also means no nuisance due to eliminated diisocyanate. Nor does the abrasion-resistant polyester mixture of the present invention incur any significant weight 1088 on sp;nn;ng due to the elimination of diisocyanate from the poly-urethane portion of the abrasion-resistant polyester mixture of the present invention.
An increase in the melt temperature, however, leads to a distinct 1088 of weight of the abrasion-resistant polyester mixture of the present invention as a conse-quence of unacceptable elimination of diisocyanates.
Thermogravimetric studies of the abrasion-resistant polyester mixture of the present invention have shown that the temperature range of up to not more than 250C, in which the sp; nn; ng of the polyester mixture of the present invention takes place, results in a 1088 of substance of only about 0.3% by weight (without moisture 1088), whereas the sp;nn;ng temperature of the known polyethylene terephthalate/polyurethane mixtures (~ 290C) gives rise to a 1088 of substance above 3% by weight.
The filament thus produced is then subjected to an afterdraw, preferably in a plurality of stages, in particular in two or three stages, with a total draw ratio of 1:4 to 1:8, preferably 1:5 to 1:7, and subsequently heat-set at temperatures of 160 to 240C, preferably 170 to 210C, operating at constant length or with a permitted shrinkage of 10 to 30%, preferably 15 to 25%, being possible.
The resulting copolyester monofilaments of the present invention have an excellent abrasion-resistance. For instance, under the abrasion test described below a 21~5470 monofilament according to the present invention which iB
composed of the abra~ion-resistant polyester mixture according to the present invention lo~e~ only a fraction of the weight which a conventional polyester yarn for industrial use loses under the ~ame test conditions.
The abrasion t~n~ency was measured as follows:
10,000 m of monofil were pulled at 100 m/min through a weighed test device consisting of a grid of 20 metal wires having a wire diameter of 0.5 mm and spaced 2 mm apart and a collecting dish for abraded-off material, situated underneath the grid and firmly connected to the grid. After the monofilament has pa~ed through, the test device (consi~ting of grid ~ receiving dish) is reweighed. Any increase in the weight of the test device is due to abraded-off material and ie a measure of the abrasion resistance.
The present invention further provides paper machine wire cloths containing the abrasion-resistant monofilaments of the present invention or compri~ing the abrasion-resistant monofilaments of the pre~ent invention asabrasion-resistant component, and the use of these mono-filaments in or for the production of paper machine wire cloths, especially of the endless type.
Such a forming fabric in a paper machine generally has a single- to three-layer construction and a basi~ weight of 100 to 800, preferably 200 to 600, g/m2. It is construc-ted from monofilaments having a linear density preferably within the range from 157 to 2,200 dtex. The monofila-ments used according to the present invention have a modulus of elasticity of greater than 5 N/tex, a tenacity of 20 to 30 cN/tex, a bre~;ng exten~ion of 50 to 70% and a 180C hot air shrinkage of 15 to 40%.
The monofilaments are woven up to the paper machine wire cloths on conventional full-width weaving machines using the machine parameter~ also cuRtomary in the weaving of polyethylene terephthalate. For instance, good wire cloth 214~470 fabric i8 obtained on weaving monofills having a diameter of 0.17 mm in warp with face wefts of 0.2 mm and back wefts of 0.22 mm. The fabric possesses very good dimen-sional stability and abrasion resistance.
However, paper machine wire cloths having superior abrasion properties can be obtained if the abrasion-resistant monofilaments of the present invention are included only in an effective proportion, in which case it is advantageous for the areas of the wire cloth which are exposed to a particularly high abrasion to be rich in the filaments of the present invention. The fabric obtained is generally aftertreated in an appropriately dimensioned heat-setter in order that the specific wire cloth properties desired in an individual case may be conferred.
The paper machine wire cloth fabric produced in this way from or with monofilaments of the present invention has better abrasion resistance and hence a significantly longer life in the paper machine compared with material produced from conventional polyethylene terephthalate monofilaments.
The Examples which follow illustrate the production of monofilaments according to the present invention and their appreciably improved abrasion characteristics compared with conventional polyethylene terephthalate monofilaments.
ExamPle 1 An abrasion-resistant polyester mixture according to the present invention is produced by mix~ng 85 parts by weight of a polyethylene terephthalate isophthalate having a proportion of lO mol% of isophthalic acid in the polyester chain and a melting point of 229C with 15 parts by weight of ~DESMOPAN VPRA 8392.
The mixture is introduced into an extruder, where it is melted and homogenized. The melt temperature at the 2145~7~
.
extruder exit is 225C. Using a sp;nn;ng pump this melt is forced under a pressure of 220 bar through spinneret holes 0.6 mm in diameter and consolidated in a cooling bath using hot water at 70C. The monofilaments thus obtained are then drawn in two stages, using a draw ratio of 5.8 in the first stage and of 1.1 in the second stage.
The monofilament is then set at 200C with 21% shrinkage being permitted.
The wound-up monofilaments have a diameter of 0.2 mm, a breaking strength of 23 cN/tex at a break;ng extension of 65%, and a residual shrinkage at 180C of 15% (with a shrinkage force of 12 cN).
Exam~le 2 A mixture of 70 parts by weight of chips of the iso-phthalic acid-modified polyethylene terephthalate used in Example 1 and 30 parts by weight of chips of ~DESMOPAN
VPKA 8392 is melted in an extruder to form a hot melt at 230C. A sp;nn;ng pump forces this melt through spinneret holes 0.8 mm in size. The monofills obtained are cooled in hot water at 70DC and then drawn in two stages using a first stage draw ratio of 6.1 and a second stage draw ratio of 1.2. They are then set at 180C with 21% of shrinkage being permitted. The ready-produced mono-filament has a diameter of 0.2 mm. The breAk; ng strength is 25 cN/tex at a breAk; ng extension of 60%. The residual shrinkage at 180C is 39% with a shrinkage force of 10 cN.
The monofilaments produced according to Examples 1 and 2 of the present invention were tested in respect of abrasion resistance by the above-described method against a monofilament of the same linear density produced from the polyester used in the Examples, i.e. without polyurethane.
The test results obta~ne~ are shown in the table below.
21~5470 Table 0~ of TP~1)15% of TP~l)30~ of TP~1) Control Example l Example 2 Weight increaee of meaeuring device = 0.7 0.2 c 0.1 abraded-off material ~mgl 1) TP~ = ~hr plaetic polyur-thane
Abrasion-resistant polyester mixture with ~nh~nced consistency of processing, monofilaments therefrom, and production and use thereof The present invention relates to an abrasion-resistant polyester mixture with enh~nced consistency of proces-sing, to monofilaments spun therefrom, which can be used with particular advantage for producing paper machine wire cloths, and to the production and use thereo$.
Synthetic fibers and fil ments and also sheetlike materials therefrom, such as woven or knitted fabrics, which are to be used for technical applications are generally exposed to far higher stresses than fiber materials for purely textile applications, for example in the clothing sector.
A very typical application for technical fiber materials is the production of paper machine wire cloths. Paper machine wire cloths are exposed in use to a ben~;ng and stretching stress, constant flection, high temperatures in a moist environment and a high abrasive stress.
Even in these mechanical and chemical stresses, paper machine wire cloths must keep their strength, dimensional stability and planarity for as long as possible; that is, they may also only show minimal swelling due to water absorption.
It is especially the abrasive stress, due on the under-side to rubbing of the wire cloths against support elements of the paper machine and against sealing elements above the suction boxes, where the paper web is drained, and on the inside of the wire cloths to rubbing of the filaments against each other and to the flow-through of water cont~;n;ng abrasive paper filler, which has a very great effect on wire cloth life.
It has proved to be extremely difficult to provide a wire cloth material which is sufficiently resistant to all the stresses mentioned.
2145~70 The original Fourdrinier papermaking machine wire cloths were in fact made of metal wires, the metal used being phosphorus bronze.
Although these metal wires are very resistant to the high temperatures and the hydrolytic attack, they have unsatisfactory abrasion characteristics. It has also already been proposed to make paper machine wire cloth~
from polyester filaments, especially polyethylene or polybutylene terephthalate filaments, or from polyamide filaments, for example nylon-6 or nylon-6,6 filaments.
It is true that polyester filaments possess good dynamic stability and, because of their low moisture regain, good dimensional stability, but their chemical resistance at high temperatures generally leaves something to be desired, and their abrasion resistance in particular does not meet the requirements of papermaking machine manufacturers.
Polyamide filaments, by contrast, do show good abrasion resistance, but have a high moisture regain coupled with high swelling and low dimensional stability.
Various publications, for example US-A-4 529 013, US-A-4 289 173 and DE-A-2 502 466, have already described attempts to combine polyester and polyamide filaments to produce paper machine wire cloths which are better equipped to meet the high requirements.
However, these attempts have only been partially suc-cessful; more particularly, new difficulties arise as a result of using different filament materials in one and the same fabric.
Another way was proposed in EP-A-0 387 395, which recom-mends weaving paper machine wire cloths from polyester filaments, especially polyethylene terephthalate fila-ments, using a weft consisting at least partly of filaments of a polyester cont~;ning 10 to 40% by weight of a thermoplastic urethane and up to 5% by weight of a hydrolysis stabilizer.
A similar proposal is known from DE-T-3 249 110, which recommends producing filaments for paper machine wire cloths from a mixture of a polyester, a polyester stabilizer and a "thermoplastic material", wherein the "thermoplastic material" used is said to be a thermo-plastic polyurethane or a polyether-ester block copolymer.
It is stated in both documents that these polyester mixtures result in filaments of improved hydrolysiR
resistance and improved abrasion resistance.
However, a serious disadvantage of these known polyester mixtures is that melt sp; nn; ng these mixtures gives rise to the formation, in the melt, of gas bubbles which reduce the consistency of processing. This evolution of gas is presumably due to the onset of the decomposition of the polyurethane component.
It has now been found that it is possible to produce polyester mixtures which are processible, especially spinnable, without noticeable gas evolution and which are spinnable into the filaments which combine the good mechanical properties of polyester with appreciably improved abrasion characteristics.
The present invention accordingly provides an abrasion-resistant polyester mixture with onh~nced consistency of processing, comprising a thermoplastic polyester and a thermoplastic polyurethane with or without customary nonpolymeric additives, the mixture of said polyester and said polyurethane having a melting point be_ween 200 and 230C.
The polymer material of the abrasion-resistant polyester mixture of the present invention contains from 60 to 95% by weight, preferably from 70 to 90% by weight, of said thermoplastic polyester and from 5 to 40% by weight, preferably from 10 to 30% by weight, of said thermoplastic polyurethane.
The thermoplastic polyester of the abrasion-resistant polyester mixture of the present invention has a glass 2145~70 transition point of 68 to 82C, preferably 72 to 80C, a crystallization point of 135 to 155C, preferably 140 to 150C, and a melting point within the range from 175C to 235C.
The melting point range of the abrasion-resistant poly-ester mixture of the present invention and the tem-perature ranges of the glass transition point, of the crystallization point and of the melting point of the thermoplastic polyester present in the abrasion-resistant polyester mixture of the present invention are based on a measurement in a differential sc~nn;ng calorimeter (DSC) at a temperature rise rate of 10C per minute.
The polyester of the abrasion-resistant polyester mixture of the present invention preferably has a melt viscosity of 445 to 482 Pa.s, preferably 455 to 475 Pa.s, especi-ally of 460 to 468 Pa.s, when measured at 245 + 2C and a shear gradient of 200 + 5 8-1, and of 245 to 282 Pa.s, preferably 250 to 272, especially of 255 to 270 Pa.s when measured at the same temperature and a shear gradient of 1,200 + 5 8-1 .
The thermoplastic polyesters of the abrasion-resistant polyester mixture of the present invention consist pre-~;n~ntly, i.e. at least 70 mol%, based on the totality of all polyester units, of common units derived from aromatic dicarboxylic acids and from aliphatic diols.
Common aromatic dicarboxylic acid unit~ are derived from benzenedicarboxylic acids, especially terephthalic acid and isophthalic acid; common diols have 2-4 carbon atoms, and ethylene glycol is particularly ~uitable.
The remaining 30 mol%, based on the totality of all polyester units, are then made up of dicarboxylic acid units and diol units which differ from the aromatic units forming the predominant portion of the units and which act as modifiers and make it possible for the person skilled in the art to influence the physical and chemical properties of the filaments in a specific manner.
21~47~
Examples of such dicarboxylic acid units are radicals of aromatic dicarboxylic acids differing from the aromatic dicarboxylic acid units forming the pre~om;nAnt portion of the dicarboxylic acid units, or radical~ of arali-phatic dicarboxylic acids having one or more, preferablyone or two, fused or unfused aromatic nuclei, for example of isophthalic acid, 5-sulfoisophthalic acid, 5-sulfopro-poxyisophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, p-phenylenediacetic acid, 4,4'-oxydiphenyldicarboxylic acid or diphenoxyalkanedi-carboxylic acid, or radicals of cyclic or acyclic aliphatic dicarboxylic acids, for example trans-hexa-hydroterephthalic acid, 1,2-cyclobutane~;carboxylic acid, glutaric acid, adipic acid, sebacic acid; examples of modifying diol radicals are those of branrhe~ and/or long-chain diols having 3 to 10, preferably 3 to 6, carbon atoms, for example of 1,3-propanediol, 1,4-butanediol, 1,6-h~Yane~;ol, 2,2-dimethylpropanediol or 2-ethyl-1,6-hexanediol, or of cyclic diols, for example of 1,4-hydroxymethylcyclohexane, or of diols that contain ether groups, for example of diethylene or triethylene glycol, or, if present in a small a_ount, of polyglycol having a molecular weight of about 500-2,000.
Particular preference for use as constituents of the abrasion-reQistant polye~ter mixture of the present invention is given to those thermoplastic polyesters whose polymer rha;n~, based on the totality of all polyester units, is composed of 35 to 47 mol% of units of the formula -C0-Al-C0- (I) 3 to 15 mol% of units of the formula -C0-A2-C0- (II) 35 to 50 mol% of units of the formula -0-Dl-0- (III) 0 to 15 mol% of units of the formula -o-D2-0- (IV) where A1 denotes aromatic radicals having 5 to 12, preferably 6 to 10, carbon atoms, A2 denotes aromatic radicals differing from Al or arali-phatic radicals having 5 to 16, preferably 6 to 12, 21~5~70 carbon atoms or cyclic or acyclic aliphatic radicals having 2 to 10 carbon atoms, preferably 4 to 8 carbon atoms, Dl denotes alkylene or polymethylene groups having 2 to 4 carbon atoms or cycloalkane or dimethylenecycloalkane groups having 6 to 10 carbon atoms, D2 denotes non-D~ alkylene or polymethylene groups having 3 or 4 carbon atoms or cycloalkane or dimethylenecycloalkane groups having 6 to 10 carbon atoms or straight chain or branched alkanediyl groups having 4 to 16, preferably 4 to 8, carbon atoms or radicals of the formula -(C2H4-O)m-C2H4-, where n is an integer from 1 to 40, with m = 1 or 2 being preferred for proportions of up to 20 mol% and groups with m = 10 to 40 preferably being present only in proportions of below 5 mol%.
The polyesters present in the polyester mixture of the present invention have a relative viscosity of advan-tageously 1.6 to 2.2, preferably 1.8 to 2.0, measured in a 1% strength by weight solution of the polyesters in dichloroacetic acid at 25C.
Preferred aryl Al is 1,4-phenylene, preferred aryl A2 is in particular 1,3-phenylene or else 1,4-, 1,5-, 1,8-, 2,6- and 2,7-naphthylene, 4,4'-biphenylene, furylene or a radical of the formula VI
~Z ~ ~1) where Z is polymethylene or alkylene of 1 to 4 carbon atoms, -SO2-, -C00-, -0- or -S-.
Radicals denoted by Al and A2 can all be identical within the scope of the definition given, or they can be different.
More particularly, the abovementioned radicals represen-ted by Al can be present in the polyester chain indi-vidually or mixed. It is preferable for Al to be formed 21~470 by only one or two members of the group of radicals specified for A1. Any desired further modification of the polyester chain is then preferably effected through other units within the scope of the definition for A2.
For instance, the aromatic radicals A1 can all be 1,4-phenylene radicals or they can be composed for example in a molar ratio of 4:6 to 6:4 of 2,6-naphthylene radicals and 4,4'-biphenyldiyl radicals.
Preference iB given to polyesters in which A1 i~
1,4-phenylene and especially to those in which A2 is likewise aryl.
Similarly, the radicals denoted by D1 and D2 can all be identical within the scope of the definition given, or they can be different.
More particularly, the abovementioned radicals represen-ted by D1 can be present in the polyester chain indi-vidually or mixed. It is preferable for D1 to be formed by only one or two members of the group of radicals specified for D1. Any desired further modification of the polyester chain is then preferably effected through other units within the scope of the definition for D2.
For instance, the radicals D1 can all be ethylene radi-cals or they can be composed for example in a molar ratio of lO:1 to 1:10 of ethylene-1,4-dimethylenecyclo~eYAne radicals.
Particular preference is given to polyesters in which is exclusively ethylene.
Particular preference is further gi~en to polyesters in which A1 is 1,4-phenylene and A2 is 1,3-phenylene.
Particular preference is further given to polyesters with 40 to 47 mol% of units of the formula I, 3 to 10 mol% of units of the formula II, 48 to 50 mol%, especially 50 mol%, of units of the formula III and 0 to 2, especi-ally 0, mol% of units of the formula IV.
The nuclei of the aromatic and araliphatic radicals represented by A1 and A2 may in turn additionally carry one or two substituents. In this case, however, it is preferable for only a proportion of up to 15%, especially up to 7%, of the aromatic radicals present to be substi-tuted. Preferably, the substituted aromatic radicals eachcarry only one substituent. Particularly suitable sub-stituents are alkyl having 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and sulfo.
Radicals derived from aliphatic dicarboxylic acids and aromatic radicals which yield angled chA;nR, for example isophthalic radicals, or which comprise rather bulky aromatic nuclei, such as the naphthalene nucleus, and also the long-chain groups Y are incorporated in parti-cular into the polyester chain when a further modifi-cation of the properties of the polyester is desired.
Preference is given to polyesters which contain less than7% of these modifying components.
The thermoplastic polyurethane present in the abrasion-resistant polyester mixture of the present invention is primarily characterized by application-specific physical properties.
It preferably has a shear modulus of 8 to 80 MPa, prefer-ably 20 to 50 MPa, within the temperature range from 20 to 60C, a mechanical 1088 factor tan(~) of 0.8*10-2 to 1.2*10-within the temperature range from 20 to 60C, a Shore A hardness, measured in accordance with DIN 53505, of 82 to 100, and a Shore D hardness, measured in accordance with DIN 53505, of 30 to 60.
It is further preferable for the thermoplastic polyurethane of the abrasion-resistant polyester mixture of the present .nvention to have a tensile strength, measured in accordance with DIN 53504, of 32 to 42 MPa, a breA~;ng extension, measured in accordance with DIN 53504, of 420 to 520% and an impact toughnes6, measured in accordance with DIN 53515 of 32 to 45%.
214517~
-g The thermoplastic polyurethane of the abrasion-re~istant polyester mixture of the present invention conforms to the idealized formula V
--O-CO-NH-R1-NH-CO-O-R2 (v) -n where Rl is a bivalent, aromatic or aralipha~ic radical of 6 to 18 carbon atoms with a substituted or unsubstituted aromatic ring or with two fused or unfused, substituted or unsubstituted aromatic rings, R2 is a polyether unit of the formula VI
O- CH2- CH O-- (Vl) -m where X3 is hydrogen or methyl, and m is from 10 to 100, preferably from 10 to 30, or the radical of polytetra-hydrofuran or preferably a polyester unit of the formula VII
~ _ _ --o-R3-o-Co-R4-Co ~R3~_ -p- -r (Vll) where R3 is straight-chain or optionally branched alkane-diyl or oxaalkanediyl having 2 to 8, preferably 2 to 6, carbon atoms, for example ethylene, 1,3-propanediyl, 1,4-but~ne~;yl, 1,6-hexanediyl, 2-ethyl-1,6-hexanediyl, 2,2-dimethyl-1,3-propanediyl, or the bivalent ox~ ne-diyl radicals derived from diethylene glycol or triethy-lene glycol, R4 iB alkanediyl having 2 to 6, preferably 2 to 4, carbon atoms, cycloalkanediyl such as 1,4- or 1,3-cyclohexane-diyl or a bivalent aromatic radical ha~ing 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, especially 1,3-or 1,4-phenylene, p i~ a number 80 that R4 has a molecular weight of 1,000 to 2,000 (p = 5 to 12, preferably 8 to 11) and q is either 0 or 1.
The polyurethane present in the abrasion-resistant polyester mixture of the present invention was said above to conform to an n idealized~ formula. This means that the formula does not strictly reflect the real structure of the polyurethane. Polyurethanes, as is be known, are produced by reacting diisocyanates with hydroxyl-cont~;n;ng polyethers or polyesters. The high reactivityof the diisocyanates, howe~er, may also gi~e rise, to a minor extent, to secondary reactions which lead to products whose structure is not described by the indi-cated formula.
Nevertheless, the idealized formula is, to the person skilled in the art, a completely adequate description of the polyurethane used, since it reveals which starting materials were combined to form the product in question.
The person skilled in the art is thus enabled by the formula to prepare the thermoplastic polyurethane present in the abrasion-resistant polyester mixture of the present invention.
The abrasion-resistant polyester mixture of the present invention preferably comprises a thermoplastic poly-urethane of the idealized formula V where R1 is pheny-lene, naphthalene or a unit of the formulae VIII or IX
~X1- ~3X2~
Vlll IX
which may each carry substituents, where Xl is a bivalent aliphatic radical having 1 to 3 carbon atoms and x2 is a direct bond, a bivalent aliphatic radical having 1 to 3 carbon atoms, -CO-, -SO2-or -NH-CO-NH-.
Particular preference is given to those abrasion-resistant polyester mixtures of the present invention which comprise a thermoplastic polyurethane of the idealized formula V
where Rl i8 a unit of the formula X
~CH2~ ~
The aromatic rings present in the thermoplastic polyurethane may be unsubstituted or carry one or two substituents selected from the group consisting of -SO3H
and -CH3.
Some thermoplastic polyurethanes having the above-indicated features are commercially available.
A polyurethane which i8 very suitable for use aR a constituent of the abrasion-resistant polyester mixture of the present invention is for example ~DESMOPAN VPRA 8392 from-BAYER AG.
The abrasion-resistant polyester mixture ol the present invention may comprise up to 10% by weight of non-polymeric substances, such as modifiers, fillers, pig-ments, dyes, antioxidants, hydrolysis, light and temperature stabilizers and/or processing aids.
Particularly preferred abrasion-resistant polyester mixtures of the present invention comprise in particular up to 10% by weight, preferably up to 5% by weight, of polyester stabilizers which protect the polyester in the mixture against hydrolysiE and thermal degradation.
Of particular advantage for use as stabilizers are those compounds capable of reacting with the ter~; n~ 1 carboxyl groups of the polyester to form nonacid end groups, for example glycidyl ethers, keteneimines, aziridines, iso-cyanates. Of particular advantage for use as stabilizers are carbodiimides and polycarbodiimides, especially if used combined with one another.
The abrasion-resistant polyester mixtures of the present invention are homogeneous mixtures of the mixture com-ponents. "Homogeneous" for the purposes of this inven-tion, however, is not restricted to solution-like, i.e.
molecularly diRperse, distributions, but the mixture may also consist of a uniform mixture of the pulverulent ingredients or of a uniform mixture of pellets or chips of the mixture constituents.
What matters is merely that the mixtures can be melted in an extruder to form a melt which retains the same com-position during extrusion, thus always producing an extrudate of unambiguously defined composition.
In the case of abrasion-resistant polyester mixtures of the present invention which consist of a homogeneous mixture of powders or even larger particles, for example pellets, any nonpolymeric constituents of the abrasion-resistant polyester mixture of the present invention willgenerally be located in the particles of the polyester and/or of the polyurethane, preferably in the polyester particles.
The abrasion-resistant polyester mixture of the present invention is produced by mixing the above-described thermoplastic polyesters and polyurethanes in suitable known mixing apparatus, for example mixing drums or 211547~
kneaders. These polymeric constituents can be present in solid form, for example as powders, chips or pellets, or as melts. It is of course also possible to stir a pulverulent ingredient into a melt of the other. The choice of mixing apparatus is made on the basis of suitability for the job in hand; that is, the chosen mixing apparatus must be adapted to the physical state of the ingredients to be mixed.
If the ingredients melt in the course of being mixed, which given thorough ~;Y;ng of the melt leads to particu-larly good or even molecularly disperse homogenization of the abrasion-re~istant polyester mixture of the present invention, extrusion and pelletization of the melt can be used to obtain the abrasion-resistant polyester mixture of the present invention in the form of uniform pellets or chips.
Nonpolymeric ingredients are generally incorporated into one or both of the polymer components, preferably into the polyester component.
A particularly advantageous embodiment of producing the abrasion-resistant polyester mixture of the present invention, comprises combining the polymer components, which may contain nonpolymeric ingredients already present, in the desired mixing ratio immediately upstream of the extruder inlet. Homogenization of the mixture is then effected in the feeding and mixing zone of the extruder screw. The material mixed and homogenized in the extruder can then be extruded directly to the desired articles, preferably the monofilaments of the present invention.
The present invention further provides monofilaments consisting of the above-described abrasion-resistant polyester mixture of the present invention.
These monofilaments have a linear density of 70 to 40,000 dtex, preferably 157 to 2,200 dtex, an initial modulus of 400 to 800, preferably 500 to 700, cN/tex, a tenacity of 15 to 30, preferably 20 to 30, cN/tex, a 21~5470 bre~king extension of 50 to 70%, preferably 60 to 65%, a 180C dry heat shrinkage of 10 to 40%, preferably 15 to 20%, with the development of a shrinkage tension of 0.1 to 0.5, preferably 0.2 to 0.3, cN/tex, and a boil off shrinkage of 3 to 10%, preferably 4 to 7%.
The monofilaments can be produced with different cross-~ectional shapes, including as hollow filaments. A round cross section is preferred.
These monofilaments can be used with particular ad~antage for the production of paper machine wire cloths.
To produce the monofilament~ of the pre~ent invention, the abrasion-resistant polyester mixture of the pre~ent invention i~ dried directly prior to sp;nn;ng, preferably by heating in a dry atmosphere or under reduced pre~sure.
Thereafter the abra~ion-resistant polyester mixture of the present invention is melted and homogenized in an extruder. Alternatively, as stated above, the thermo-plastic polyester and the polyurethane components of the abrasion-resistant polyester mixture of the present invention can also be separately predried and fed into the extruder in the de~ired mixing ratio.
The melt completely homogenized in the extruder i~
filtered in a customary spin pack and extruded through a ~pinneret at a melt temperature of 185 to 245C, prefer-ably 210 to 235C. The extruded molten filament is cooled in a spin bath (for example water at about 70C) and wound up or taken off at a speed which is greater than the extru~ion speed of the copolyester melt 80 that a drawdown of 1:2 to 1:4, preferably 1:2.5 to 1:3.5, results.
The extrusion speed is advantageously set in such a way that, in the interests of economical production of the monofilaments of the present invention, a sp;nn;ng take-off speed of 5 to 30, preferably 15 to 25, m per minute can be used.
2145~70 Of particular importance for the production of the mono-filaments of the present invention i8 the maintenance of the melt temperature range mentioned above. This tempera-ture ensures the production of filaments which are in accordance with the present invention and have optimum application properties. This temperature range also means no nuisance due to eliminated diisocyanate. Nor does the abrasion-resistant polyester mixture of the present invention incur any significant weight 1088 on sp;nn;ng due to the elimination of diisocyanate from the poly-urethane portion of the abrasion-resistant polyester mixture of the present invention.
An increase in the melt temperature, however, leads to a distinct 1088 of weight of the abrasion-resistant polyester mixture of the present invention as a conse-quence of unacceptable elimination of diisocyanates.
Thermogravimetric studies of the abrasion-resistant polyester mixture of the present invention have shown that the temperature range of up to not more than 250C, in which the sp; nn; ng of the polyester mixture of the present invention takes place, results in a 1088 of substance of only about 0.3% by weight (without moisture 1088), whereas the sp;nn;ng temperature of the known polyethylene terephthalate/polyurethane mixtures (~ 290C) gives rise to a 1088 of substance above 3% by weight.
The filament thus produced is then subjected to an afterdraw, preferably in a plurality of stages, in particular in two or three stages, with a total draw ratio of 1:4 to 1:8, preferably 1:5 to 1:7, and subsequently heat-set at temperatures of 160 to 240C, preferably 170 to 210C, operating at constant length or with a permitted shrinkage of 10 to 30%, preferably 15 to 25%, being possible.
The resulting copolyester monofilaments of the present invention have an excellent abrasion-resistance. For instance, under the abrasion test described below a 21~5470 monofilament according to the present invention which iB
composed of the abra~ion-resistant polyester mixture according to the present invention lo~e~ only a fraction of the weight which a conventional polyester yarn for industrial use loses under the ~ame test conditions.
The abrasion t~n~ency was measured as follows:
10,000 m of monofil were pulled at 100 m/min through a weighed test device consisting of a grid of 20 metal wires having a wire diameter of 0.5 mm and spaced 2 mm apart and a collecting dish for abraded-off material, situated underneath the grid and firmly connected to the grid. After the monofilament has pa~ed through, the test device (consi~ting of grid ~ receiving dish) is reweighed. Any increase in the weight of the test device is due to abraded-off material and ie a measure of the abrasion resistance.
The present invention further provides paper machine wire cloths containing the abrasion-resistant monofilaments of the present invention or compri~ing the abrasion-resistant monofilaments of the pre~ent invention asabrasion-resistant component, and the use of these mono-filaments in or for the production of paper machine wire cloths, especially of the endless type.
Such a forming fabric in a paper machine generally has a single- to three-layer construction and a basi~ weight of 100 to 800, preferably 200 to 600, g/m2. It is construc-ted from monofilaments having a linear density preferably within the range from 157 to 2,200 dtex. The monofila-ments used according to the present invention have a modulus of elasticity of greater than 5 N/tex, a tenacity of 20 to 30 cN/tex, a bre~;ng exten~ion of 50 to 70% and a 180C hot air shrinkage of 15 to 40%.
The monofilaments are woven up to the paper machine wire cloths on conventional full-width weaving machines using the machine parameter~ also cuRtomary in the weaving of polyethylene terephthalate. For instance, good wire cloth 214~470 fabric i8 obtained on weaving monofills having a diameter of 0.17 mm in warp with face wefts of 0.2 mm and back wefts of 0.22 mm. The fabric possesses very good dimen-sional stability and abrasion resistance.
However, paper machine wire cloths having superior abrasion properties can be obtained if the abrasion-resistant monofilaments of the present invention are included only in an effective proportion, in which case it is advantageous for the areas of the wire cloth which are exposed to a particularly high abrasion to be rich in the filaments of the present invention. The fabric obtained is generally aftertreated in an appropriately dimensioned heat-setter in order that the specific wire cloth properties desired in an individual case may be conferred.
The paper machine wire cloth fabric produced in this way from or with monofilaments of the present invention has better abrasion resistance and hence a significantly longer life in the paper machine compared with material produced from conventional polyethylene terephthalate monofilaments.
The Examples which follow illustrate the production of monofilaments according to the present invention and their appreciably improved abrasion characteristics compared with conventional polyethylene terephthalate monofilaments.
ExamPle 1 An abrasion-resistant polyester mixture according to the present invention is produced by mix~ng 85 parts by weight of a polyethylene terephthalate isophthalate having a proportion of lO mol% of isophthalic acid in the polyester chain and a melting point of 229C with 15 parts by weight of ~DESMOPAN VPRA 8392.
The mixture is introduced into an extruder, where it is melted and homogenized. The melt temperature at the 2145~7~
.
extruder exit is 225C. Using a sp;nn;ng pump this melt is forced under a pressure of 220 bar through spinneret holes 0.6 mm in diameter and consolidated in a cooling bath using hot water at 70C. The monofilaments thus obtained are then drawn in two stages, using a draw ratio of 5.8 in the first stage and of 1.1 in the second stage.
The monofilament is then set at 200C with 21% shrinkage being permitted.
The wound-up monofilaments have a diameter of 0.2 mm, a breaking strength of 23 cN/tex at a break;ng extension of 65%, and a residual shrinkage at 180C of 15% (with a shrinkage force of 12 cN).
Exam~le 2 A mixture of 70 parts by weight of chips of the iso-phthalic acid-modified polyethylene terephthalate used in Example 1 and 30 parts by weight of chips of ~DESMOPAN
VPKA 8392 is melted in an extruder to form a hot melt at 230C. A sp;nn;ng pump forces this melt through spinneret holes 0.8 mm in size. The monofills obtained are cooled in hot water at 70DC and then drawn in two stages using a first stage draw ratio of 6.1 and a second stage draw ratio of 1.2. They are then set at 180C with 21% of shrinkage being permitted. The ready-produced mono-filament has a diameter of 0.2 mm. The breAk; ng strength is 25 cN/tex at a breAk; ng extension of 60%. The residual shrinkage at 180C is 39% with a shrinkage force of 10 cN.
The monofilaments produced according to Examples 1 and 2 of the present invention were tested in respect of abrasion resistance by the above-described method against a monofilament of the same linear density produced from the polyester used in the Examples, i.e. without polyurethane.
The test results obta~ne~ are shown in the table below.
21~5470 Table 0~ of TP~1)15% of TP~l)30~ of TP~1) Control Example l Example 2 Weight increaee of meaeuring device = 0.7 0.2 c 0.1 abraded-off material ~mgl 1) TP~ = ~hr plaetic polyur-thane
Claims (22)
1. An abrasion-resistant polyester mixture with enhanced consistency of processing, comprising a thermoplastic polyester and a thermoplastic poly-urethane with or without customary nonpolymeric additives, the mixture of said polyester and said polyurethane having a melting point between 200 and 230°C.
2. The abrasion-resistant polyester mixture of claim 1 comprising up to 10% by weight of nonpolymeric substances, such as modifiers, fillers, pigments, dyes, antioxidants, hydrolysis, light and tempera-ture stabilizers and/or processing aids.
3. The abrasion-resistant polyester mixture of at least one of claims 1 and 2 wherein the polymer material contains from 60 to 95% by weight, preferably from 70 to 90% by weight, of said thermoplastic polyester and from 5 to 40% by weight, preferably from 10 to 30%
by weight, of said thermoplastic polyurethane.
by weight, of said thermoplastic polyurethane.
4. The abrasion-resistant polyester mixture of at least one of claims 1 to 3 wherein the polyester has a glass transition point of 68 to 82°C, preferably 72 to 80°C, a crystallization point of 135 to 155°C, preferably 140 to 150°C, and a melting point within the range from 175°C to 235°C.
5. The abrasion-resistant polyester mixture of at least one of claims 1 to 4 wherein the polyester has a melt viscosity of 445 to 482 Pa.s, preferably 455 to 475 Pa.s, especially of 460 to 468 Pa.s, when measured at 245 ? 2°C and a shear gradient of 200 ? 5 s-1, and of 245 to 282 Pa.s, preferably 250 to 272, especially of 255 to 270 Pa.s when measured at the same temperature and a shear gradient of 1,200 ? 5 s-1.
6. The abrasion-resistant polyester mixture of at least one of claims 1 to 5 wherein the polyester contains at least 70 mol%, based on the totality of all polyester units, of units derived from aromatic dicarboxylic acids and from aliphatic diols, and not more than 30 mol%, based on the totality of all polyester units, of dicarboxylic acid units differ-ing from the aromatic dicarboxylic acid units forming the predominant portion of the dicarboxylic acid units, or radicals derived from araliphatic dicarboxylic acids having one or more, preferably one or two, fused or unfused aromatic nuclei, or from cyclic or acyclic aliphatic dicarboxylic acids having 4 to 12 carbon atoms and diol units derived from branched and/or long-chain diols having 3 to 10, preferably 3 to 6, carbon atoms, or of cyclic diols, or of diols that contain ether groups, or, if present in a small amount, of polyglycol having a molecular weight of about 500-2,000.
7. The abrasion-resistant polyester mixture of at least one of claims 1 to 6 wherein the polyester, based on the totality of all polyester units, is composed of 35 to 47 mol% of units of the formula -CO-A1-CO- (I) 3 to 15 mol% of units of the formula -CO-A2-CO- (II) 35 to 47 mol% of units of the formula -O-D1-O- (III) 3 to 15 mol% of units of the formula -O-D2-O- (IV) where A1 denotes aromatic radicals having 5 to 12, prefer-ably 6 to 10, carbon atoms, A2 denotes aromatic radicals differing from A1 or araliphatic radicals having 5 to 16, preferably 6 to 12, carbon atoms or cyclic or acyclic aliphatic radicals having 2 to 10 carbon atoms, preferably 4 to 8 carbon atoms, D1 denotes alkylene or polymethylene groups having 2 to 4 carbon atoms or cycloalkane or dimethylene-cycloalkane groups having 6 to 10 carbon atoms, D2 denotes non-D1 alkylene or polymethylene groups having 3 or 4 carbon atoms or cycloalkane or dimethylenecycloalkane groups having 6 to 10 carbon atoms or straight-chain or branched alkanediyl groups having 4 to 16, preferably 4 to 8, carbon atoms or radicals of the formula -(C2H4-O)m-C2H4-, where n is an integer from 1 to 40, with m = 1 or 2 being preferred for proportions of up to 20 mol% and groups with m = 10 to 40 preferably being present only in proportions of below 5 mol%.
8. The abrasion-resistant polyester mixture of at least one of claims 1 to 7 wherein the polyesters present therein have a relative viscosity from 1.6 to 2.2, preferably from 1.8 to 2.0, measured in a 1%
strength by weight solution of the polyesters in dichloroacetic acid at 25°C.
strength by weight solution of the polyesters in dichloroacetic acid at 25°C.
9. The abrasion-resistant polyester mixture of at least one of claims 1 to 8 wherein the polyurethane has a shear modulus of 8 to 80 MPa, preferably 20 to 50 MPa, within the temperature range from 20 to 60°C, a mechanical loss factor tan(.delta.) of 0.8*10-2 to 1.2*10-1 within the temperature range from 20 to 60°C, a Shore A hardness, measured in accordance with DIN 53505, of 82 to 100, a Shore D hardness, measured in accordance with DIN 53505, of 30 to 60, a tensile strength, measured in accordance with DIN 53504, of 32 to 42 MPa, a breaking extension, measured in accordance with DIN 53504, of 420 to 520%
and an impact toughness, measured in accordance with DIN 53515 of 32 to 45%.
and an impact toughness, measured in accordance with DIN 53515 of 32 to 45%.
10. The abrasion-resistant polyester mixture of at least one of claims 1 to 9 wherein the thermoplastic polyurethane conforms to the idealized formula V
(V) where R1 is a bivalent, aromatic or araliphatic radical having 6 to 18 carbon atoms with a substituted or unsubstituted aromatic ring or with two fused or unfused, substituted or unsubstituted aromatic rings, R2 is a polyether unit of the formula VI
(VI) where X3 is hydrogen or methyl, and m is from 10 to 100, preferably from 10 to 30, or the radical of poly-tetrahydrofuran or preferably a polyester unit of the formula VII
(VII) where R3 is straight-chain or optionally branched alkanediyl or oxaalkanediyl having 2 to 8, prefer-ably 2 to 6, carbon atoms, for example ethylene, 1,3-propanediyl, 1,4-butanediyl, 1,6-hexanediyl, 2-ethyl-1,6-hexanediyl, 2,2-dimethyl-1,3-propane-diyl, or the bivalent oxaalkanediyl radicals derived from diethylene glycol or triethylene glycol, R4 is alkanediyl having 2 to 6, preferably 2 to 4, carbon atoms, cycloalkanediyl such as 1,4- or 1,3-cyclohexanediyl or a bivalent aromatic radical having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, especially 1,3- or 1,4-phenylene, p is a number so that R4 has a molecular weight of 1,000 to 2,000 (p = 5 to 12, preferably 8 to 11) and q is either 0 or 1.
(V) where R1 is a bivalent, aromatic or araliphatic radical having 6 to 18 carbon atoms with a substituted or unsubstituted aromatic ring or with two fused or unfused, substituted or unsubstituted aromatic rings, R2 is a polyether unit of the formula VI
(VI) where X3 is hydrogen or methyl, and m is from 10 to 100, preferably from 10 to 30, or the radical of poly-tetrahydrofuran or preferably a polyester unit of the formula VII
(VII) where R3 is straight-chain or optionally branched alkanediyl or oxaalkanediyl having 2 to 8, prefer-ably 2 to 6, carbon atoms, for example ethylene, 1,3-propanediyl, 1,4-butanediyl, 1,6-hexanediyl, 2-ethyl-1,6-hexanediyl, 2,2-dimethyl-1,3-propane-diyl, or the bivalent oxaalkanediyl radicals derived from diethylene glycol or triethylene glycol, R4 is alkanediyl having 2 to 6, preferably 2 to 4, carbon atoms, cycloalkanediyl such as 1,4- or 1,3-cyclohexanediyl or a bivalent aromatic radical having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, especially 1,3- or 1,4-phenylene, p is a number so that R4 has a molecular weight of 1,000 to 2,000 (p = 5 to 12, preferably 8 to 11) and q is either 0 or 1.
11. The abrasion-resistant polyester mixture of at least one of claims 1 to 8 wherein the thermoplastic polyurethane conforms to the idealized formula V
where R1 is phenylene, naphthylene or a unit of the formulae VIII or IX
VIII IX
which may each carry substituents, where X1 is a bivalent aliphatic radical having 1 to 3 carbon atoms and X2 is a direct bond, a bivalent aliphatic radical having 1 to 3 carbon atoms, -CO-, -SO2- or -NH-CO-NH-.
where R1 is phenylene, naphthylene or a unit of the formulae VIII or IX
VIII IX
which may each carry substituents, where X1 is a bivalent aliphatic radical having 1 to 3 carbon atoms and X2 is a direct bond, a bivalent aliphatic radical having 1 to 3 carbon atoms, -CO-, -SO2- or -NH-CO-NH-.
12. The abrasion-resistant polyester mixture of at least one of claims 1 to 8 wherein the thermoplastic poly-urethane conforms to the idealized formula V where R1 is a unit of the formula X
(X)
(X)
13. The abrasion-resistant polyester mixture of at least one of claims 1 to 8 wherein the thermoplastic poly-urethane conforms to the idealized formula V when the aromatic rings present therein are unsubstituted or carry one or two substituents selected from the group consisting of -SO3H and -CH3.
14. An abrasion-resistant monofilament with enhanced consistency of processing, having an initial modulus of greater than 5 N/tex at 25°C.
15. The abrasion-resistant monofilament of claim 14 having a tenacity of 20 to 30 cN/tex and a breaking extension of 50 to 70%.
16. The abrasion-resistant monofilament of at least one of claims 14 and 15 having a 180°C dry heat shrinkage of 15 to 40% and a boil off shrinkage of 3 to 10%.
17. A process for producing the abrasion-resistant polyester mixture of claim 1, which comprises com-bining the polymer components, which may already contain any nonpolymeric ingredients to be present, in the desired mixing ratio immediately upstream of the extruder inlet and homogenizing the mixture in the feeding and mixing zone of the extruder screw.
18. A process for producing the monofilament of claim 14, which comprises melting an abrasion-resistant polyester mixture as claimed in claim 1 in an extruder, filtering the melt in a customary spin pack and extruding the filtered melt at a melt temperature of 185 to 245°C through a spinneret using a drawdown of 1:2 to 1:4, cooling the filament in a spin bath and winding it up or taking it off at a speed which is greater than the extrusion speed of the copolyester melt, then subjecting the filament thus produced to an afterdraw in a total draw ratio of 1:4 to 1:8 and subsequently heat-setting it at temperatures of 160 to 240°C at constant length or with a permitted shrinkage of 10 to 30%.
19. The process of claim 18 wherein the melt is spun at a melt temperature within the range from 210 to 235°C.
20. The process of at least one of claims 18 and 19 wherein the monofilament is taken off at a spinning take-off speed of 5 to 30 m per minute.
21. The use of the abrasion-resistant monofilament of claim 14 in or for paper machine wire cloths.
22. A paper machine wire cloth comprising a monofilament containing an abrasion-resistant polyester mixture as claimed in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4410399A DE4410399A1 (en) | 1994-03-25 | 1994-03-25 | Abrasion-resistant polyester blend with increased processing safety, monofilaments made of it and their production and use |
| DEP4410399.9 | 1994-03-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2145470A1 true CA2145470A1 (en) | 1995-09-26 |
Family
ID=6513849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002145470A Abandoned CA2145470A1 (en) | 1994-03-25 | 1995-03-24 | Abrasion-resistant polyester mixture with enhanced consistency of processing, monofilaments therefrom, and production and use thereof |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5700881A (en) |
| EP (1) | EP0674029B1 (en) |
| JP (1) | JP3355191B2 (en) |
| AT (1) | ATE182374T1 (en) |
| BR (1) | BR9507192A (en) |
| CA (1) | CA2145470A1 (en) |
| DE (2) | DE4410399A1 (en) |
| ES (1) | ES2136757T3 (en) |
| FI (1) | FI951389A (en) |
| WO (1) | WO1995026432A1 (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19511852A1 (en) * | 1995-03-31 | 1996-10-02 | Hoechst Trevira Gmbh & Co Kg | Heavy-duty core / sheath monofilaments for technical applications |
| DE19528191A1 (en) * | 1995-08-01 | 1997-02-06 | Basf Ag | Impact-resistant thermoplastic molding compounds |
| EP0844320B1 (en) * | 1996-11-20 | 2001-09-12 | Thomas Josef Heimbach GmbH & Co. | Melt extruded monofilament |
| DE19648884A1 (en) * | 1996-11-20 | 1998-06-04 | Heimbach Gmbh Thomas Josef | Melt extruded monofilament |
| US6043313A (en) | 1997-09-04 | 2000-03-28 | Eastman Chemical Company | Thermoplastic polyurethane additives for improved polymer matrix composites and methods of making and using therefor |
| ATE228585T1 (en) | 1998-06-18 | 2002-12-15 | Heimbach Gmbh Thomas Josef | MONOFILAMENT AND PAPER MACHINE CLOTHING MADE THEREFROM |
| DE19912371A1 (en) * | 1999-03-19 | 2000-09-21 | Hahl Filaments Gmbh & Co Kg | Monofilament synthetic fiber |
| US7799255B2 (en) * | 2003-06-30 | 2010-09-21 | Lubrizol Advanced Materials, Inc. | Melt spun elastic tape and process |
| DE602005019951D1 (en) | 2004-07-06 | 2010-04-29 | Voith Patent Gmbh | Abrasion-resistant monofilament for industrial fabrics |
| US20070001566A1 (en) * | 2005-06-30 | 2007-01-04 | D Haene Pol | Impact resistant, direct contact plasma display panel filters |
| DE102006012048A1 (en) * | 2006-03-16 | 2007-09-20 | Teijin Monofilament Germany Gmbh | Polyester threads, process for their preparation and their use |
| DE102007009117A1 (en) | 2007-02-24 | 2008-08-28 | Teijin Monofilament Germany Gmbh | Electrically conductive threads, fabrics produced therefrom and their use |
| DE102007009119A1 (en) | 2007-02-24 | 2008-08-28 | Teijin Monofilament Germany Gmbh | Electrically conductive threads, fabrics produced therefrom and their use |
| DE102007009118A1 (en) | 2007-02-24 | 2008-08-28 | Teijin Monofilament Germany Gmbh | Electrically conductive threads, fabrics produced therefrom and their use |
| DE102007050489A1 (en) * | 2007-09-21 | 2009-04-09 | K&R Textil Gmbh & Co. Kg | Textile sheet material, in particular textile fabric, having shrink properties, its use and products made therewith |
| US20090311529A1 (en) * | 2008-06-16 | 2009-12-17 | Voith Patent Gmbh | High tenacity thermoplastic polyurethane monofilament and process for manufacturing the same |
| DE102009053588A1 (en) | 2009-11-17 | 2011-05-19 | Teijin Monofilament Germany Gmbh | Abrasion resistant monofilaments |
| EP2797454A1 (en) | 2011-12-30 | 2014-11-05 | Ticona LLC | Molded polymer articles for use in low temperatures having a low rigidity factor |
| DE202012001985U1 (en) | 2012-02-25 | 2012-03-30 | Nextrusion Gmbh | Abrasion resistant monofilaments for paper machine clothing |
| WO2013169351A1 (en) | 2012-05-09 | 2013-11-14 | Ticona Llc | Polymer composition and articles for use in low temperature environments that are wear resistant |
| US9074319B2 (en) * | 2013-03-15 | 2015-07-07 | Voith Patent Gmbh | Monofilament yarn for a paper machine clothing fabric |
| DE102014009238A1 (en) | 2014-06-20 | 2015-12-24 | Perlon Nextrusion Monofil GmbH | Monofilaments with high abrasion and dimensional stability, textile fabrics thereof and their use |
| US11104641B2 (en) | 2016-03-31 | 2021-08-31 | Dow Global Technologies Llc | Biscarbodiimides and polycarbodiimides and method for their preparation |
| CN109294211A (en) * | 2018-10-26 | 2019-02-01 | 含山县领创新材料科技有限公司 | A kind of noise reduction corrosion-and high-temp-resistant polyurethane screen |
| CN116876102A (en) * | 2023-08-24 | 2023-10-13 | 深圳市骏鼎达新材料股份有限公司 | Wear-resistant PET monofilament and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2502466C3 (en) * | 1975-01-22 | 1985-05-30 | Hermann Wangner Gmbh & Co Kg, 7410 Reutlingen | Interchangeable weft paper machine screen |
| US4279801A (en) * | 1975-07-02 | 1981-07-21 | General Electric Company | Thermoplastic molding compositions of a linear polyester and a poly(ester urethane) |
| DE2646647A1 (en) * | 1975-10-20 | 1977-04-21 | Mobay Chemical Corp | POLYBUTYLENE TEREPHTHALATE / POLYURETHANE MIXTURES |
| US4289173A (en) * | 1975-10-30 | 1981-09-15 | Scapa-Porritt Limited | Papermakers fabrics |
| IT1148619B (en) * | 1981-10-09 | 1986-12-03 | Jwi Ltd | MONOFILAMENT WITH LOW CARBOXYL CONTENT FOR THE USE IN THE MANUFACTURE OF A COVER FOR PAPER DRYING MACHINES |
| JPS58225413A (en) * | 1982-06-24 | 1983-12-27 | Sanden Corp | System for controlling number of revolution of main shaft |
| NL8202894A (en) * | 1982-07-16 | 1984-02-16 | Rijksuniversiteit | POLYESTER FILAMENT MATERIAL. |
| US5110852A (en) * | 1982-07-16 | 1992-05-05 | Rijksuniversiteit Te Groningen | Filament material polylactide mixtures |
| EP0349875A3 (en) * | 1988-07-07 | 1991-09-25 | General Electric Company | Paintable elestomeric compositions |
| US5169711A (en) * | 1988-08-05 | 1992-12-08 | Jwi Ltd. | Paper makers forming fabric |
| ES2064400T5 (en) * | 1989-03-17 | 2001-03-01 | Jwi Ltd | POLYESTER FORMATION FABRIC MODIFIED BY STABILIZED POLYURETHANE. |
| DE4128274A1 (en) * | 1991-08-27 | 1993-03-04 | Basf Schwarzheide Gmbh | Thermoplastic polyurethane blends with improved properties - are prepd. by compounding thermoplastic polyurethane with a polyester and small amts. of organic di;isocyanate |
| CA2134542C (en) * | 1994-03-01 | 1998-07-07 | Asten, Inc. | Papermakers fabric of polyphthalamide monofilament |
-
1994
- 1994-03-25 DE DE4410399A patent/DE4410399A1/en not_active Withdrawn
-
1995
- 1995-03-15 EP EP95103741A patent/EP0674029B1/en not_active Expired - Lifetime
- 1995-03-15 ES ES95103741T patent/ES2136757T3/en not_active Expired - Lifetime
- 1995-03-15 AT AT95103741T patent/ATE182374T1/en active
- 1995-03-15 DE DE59506407T patent/DE59506407D1/en not_active Expired - Fee Related
- 1995-03-23 US US08/409,162 patent/US5700881A/en not_active Expired - Fee Related
- 1995-03-23 FI FI951389A patent/FI951389A/en unknown
- 1995-03-24 CA CA002145470A patent/CA2145470A1/en not_active Abandoned
- 1995-03-24 JP JP52496895A patent/JP3355191B2/en not_active Expired - Fee Related
- 1995-03-24 BR BR9507192A patent/BR9507192A/en not_active Application Discontinuation
- 1995-03-24 WO PCT/EP1995/001127 patent/WO1995026432A1/en active Search and Examination
Also Published As
| Publication number | Publication date |
|---|---|
| JP3355191B2 (en) | 2002-12-09 |
| DE4410399A1 (en) | 1995-09-28 |
| ES2136757T3 (en) | 1999-12-01 |
| FI951389A0 (en) | 1995-03-23 |
| EP0674029B1 (en) | 1999-07-21 |
| ATE182374T1 (en) | 1999-08-15 |
| EP0674029A1 (en) | 1995-09-27 |
| BR9507192A (en) | 1997-09-09 |
| FI951389A (en) | 1995-09-26 |
| DE59506407D1 (en) | 1999-08-26 |
| WO1995026432A1 (en) | 1995-10-05 |
| US5700881A (en) | 1997-12-23 |
| JPH09510748A (en) | 1997-10-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |