CN102301045A - Antistatic Ultrafine Fibers And Method For Producing The Same - Google Patents

Antistatic Ultrafine Fibers And Method For Producing The Same Download PDF

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Publication number
CN102301045A
CN102301045A CN2009801555372A CN200980155537A CN102301045A CN 102301045 A CN102301045 A CN 102301045A CN 2009801555372 A CN2009801555372 A CN 2009801555372A CN 200980155537 A CN200980155537 A CN 200980155537A CN 102301045 A CN102301045 A CN 102301045A
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China
Prior art keywords
polyester
yarn
antistatic
core
sheath
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CN2009801555372A
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Chinese (zh)
Inventor
镰田大史
中岛卓
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Teijin Frontier Co Ltd
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Teijin Fibers Ltd
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Priority claimed from JP2008302666A external-priority patent/JP2010126837A/en
Priority claimed from JP2009039190A external-priority patent/JP2010196180A/en
Application filed by Teijin Fibers Ltd filed Critical Teijin Fibers Ltd
Publication of CN102301045A publication Critical patent/CN102301045A/en
Pending legal-status Critical Current

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    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/20Combinations of two or more of the above-mentioned operations or devices; After-treatments for fixing crimp or curl
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/09Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/28Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30Conjugate filaments; Spinnerette packs therefor
    • D01D5/34Core-skin structure; Spinnerette packs therefor
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/07Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • D01F1/106Radiation shielding agents, e.g. absorbing, reflecting agents
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/02Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/16Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics using jets or streams of turbulent gases, e.g. air, steam
    • D02G1/165Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics using jets or streams of turbulent gases, e.g. air, steam characterised by the use of certain filaments or yarns
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/36Cored or coated yarns or threads
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44Yarns or threads characterised by the purpose for which they are designed
    • D02G3/441Yarns or threads with antistatic, conductive or radiation-shielding properties
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING 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
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-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
    • D04H1/54Non-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 welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/541Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
    • D04H1/5412Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres sheath-core
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2929Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Multicomponent Fibers (AREA)

Abstract

Provided are antistatic polyester ultrafine fibers of superior durability. Also provided is a method for producing the same. Antistatic polyester ultrafine fibers are endowed with a variety of properties, such as UV-blocking activity, cation dyeability, flame retardence, spun-like bulkiness, soft surface texture and spring, repellency, dry texture, natural texture and spunized appearance, wool-like texture, wrinkle resistance, water absorbency and fast dryability, by introduction of a third component to the antistatic polyester ultrafine fibers, the formation of composite fibers with other fibers, modification of the cross-sectional shape, and the like.

Description

Antistatic behaviour superfine fibre and manufacture method thereof
Technical field
The present invention relates to the polyester superfine fibre with antistatic behaviour and the manufacture method thereof of excellent in te pins of durability.In more detail, relate to can be by the 3rd composition importing or with compoundization of other fiber, the change of cross sectional shape etc. give the flexible touch on fluffy sense, surface of ultraviolet screening effect, cation dyeable, anti-flammability, spinning sample and elasticity, resilience, dry feeling, naturally sense and Si Bennaizi Texturized (ス パ Na イ ズ) outward appearance, imitate the antistatic polyester superfine fibre and the manufacture method thereof of various functions such as wool sense of touch, fold are restorative, water-absorbing fast-drying.
Background technology
In the past, carried out giving hydrophily and the trial that makes it to show antistatic behaviour, proposed to have a large amount of motions up to now polyester.Known for example have a method (Japanese Patent Publication 39-5214 communique) that cooperates poly (oxyalkylene) base system polyether compound in polyester, method (the Japanese Patent Publication 44-31828 communique that in polyester, cooperates the ionic compound of the poly (oxyalkylene) base system polyether compound of non-intermiscibility basically and organic-inorganic, Japanese Patent Publication 60-11944 communique, Japanese kokai publication sho 53-80497 communique, Japanese kokai publication sho 53-149247 communique, Japanese kokai publication sho 60-39413 communique, Japanese kokai publication hei 3-139556 communique etc.).In these methods,, be truth but the inequality of the inequality that ultra fine yarn SMIS/sheath forms, single thread fiber number causes the situation with antistatic behaviour if the single thread fiber number greater than 1.6 dtex, then has antistatic behaviour.
Yet in recent years, requirement for the quality (texture) of woven and knit goods (woven and knitted fabrics), feel, outward appearance etc. improves day by day, use ultra-fine drawn polyester yarn in the past and carry out knitting or woven (knitting or weaving) though the cloth and silk of gained can obtain soft quality, performances such as heat insulating ability, suction, hygroscopicity also improve, but the what is called that can suppress Pi crack static has the cloth and silk of antistatic behaviour and does not almost completely have, so and insufficient.Especially, motion dress material, uniform etc. cover ultraviolet ray and suppress on the purposes of static without, and the cloth and silk that can not get having antistatic behaviour is a present situation.
In addition, polyester be cannot say for sure also that dyeability is good, is had the shortcoming of the vivid degree variation of product dyed thereby with fiber as dress material.At present, in order to remedy such shortcoming, be well known that copolymerization with M-phthalic acid 5-sodium sulfonate etc. be that the composition that contains azochlorosulfonate acid alkali of representative obtains, to basic-dyeable fibre be stainability polyester (below, abbreviate cation dyeable polyester as), the fiber that comprises this polyester is used in the dress material field.
Yet these cationic dyeable polyester fibers the time are difficult to take place fusion than common polyester fiber melt viscosity height, burning and drop, so have the shortcoming of easy fire spreading, the problem that existence requires the use in the field of anti-flammability to be restricted.
In order to solve such problem, also copolymerization proposed except that the composition that contains azochlorosulfonate acid alkali there has been to propose in the polyester of specific phosphorous dicarboxyl oxygen compound, the TOHKEMY 2005-273043 communique polyester that copolymerization has specific organic phosphorus compound in the Japanese kokai publication hei 7-109621 communique.
Yet, in this method, be the acid catalyst effect that utilizes phosphorus compound, the generation of diethylene glycol (DEG) is promoted in polymerization process, because diethylene glycol (DEG) content uprises, thereby has the problem of stringiness, light resistance variation.
Further, for polyester fiber, polyester long fiber particularly, as the quality of giving like staple fiber yam as the high wool or the method for bulkiness, Japanese Patent Publication 60-11130 communique for example, Japanese Patent Publication 61-19733 communique, Japanese kokai publication hei 8-13275 communique, shown in the TOHKEMY 2006-169697 communique etc., proposed to utilize and made up the long stapled like staple fiber yam sample of the polyester false twisting 2 layers of structure yarn that have the elongation rate variance more than 2 kinds bulkiness is improved, or, spontaneous elongation polyester mutifilament yarn and heat-contractable ployester multifilament textile knit by being mixed with air nozzle, or the lax heat treatment of enforcement, on one side to the polyester mutifilament yarn that the becomes spontaneous elongation heat treatment that relaxes, spontaneous elongation polyester mutifilament yarn after this lax heat treatment is supplied with the heat-contractable ployester multifilament textile continuously on one side, and mix method (for example, Japanese kokai publication hei 1-250425 communique) of knitting etc. with air nozzle.
Yet for common stretch yarn (FOY), even have antistatic behaviour, false twisting processing as described above or air are mixed to be knitted as if carrying out, the fluffing due to twisted distortion of generation or the friction easily, thereby actual conditions are to give sufficient antistatic behaviour.
The prior art document
Patent documentation
Patent documentation 1: Japanese Patent Publication 39-5214 communique
Patent documentation 2: Japanese Patent Publication 44-31828 communique
Patent documentation 3: Japanese Patent Publication 60-11944 communique
Patent documentation 4: Japanese kokai publication sho 53-80497 communique
Patent documentation 5: Japanese kokai publication sho 60-39413 communique
Patent documentation 6: Japanese kokai publication hei 3-139556 communique
Patent documentation 7: Japanese kokai publication hei 7-109621 communique
Patent documentation 8: TOHKEMY 2005-273043 communique
Patent documentation 9: Japanese Patent Publication 60-11130 communique
Patent documentation 10: Japanese Patent Publication 61-19733 communique
Patent documentation 11: Japanese kokai publication hei 8-13275 communique
Patent documentation 12: TOHKEMY 2006-169697 communique.
Summary of the invention
The problem that invention will solve
The objective of the invention is to overcome the problem that above-mentioned prior art has, the polyester superfine fibre with antistatic behaviour and the manufacture method thereof of excellent in te pins of durability is provided.
And then the objective of the invention is to, can by import to above-mentioned antistatic polyester superfine fibre the 3rd composition, with compoundization of other fiber, the change of cross sectional shape etc., and give the flexible touch on fluffy sense, surface of ultraviolet screening effect, cation dyeable, anti-flammability, spinning sample and elasticity, resilience, dry feeling, naturally sense and Si Bennaizi Texturized (ス パ Na イ ズ) outward appearance, imitate the antistatic polyester superfine fibre and the manufacture method thereof of various functions such as wool sense of touch, fold are restorative, water-absorbing fast-drying.
Be used to solve the means of problem
That is, according to the present invention,
(1) antistatic behaviour core-sheath-type polyester superfine fibre is provided, its be core by polyester A, sheath portion by the core-sheath-type polyester complex fiber that copolyester B constitutes, it is characterized in that, satisfy following important document:
(i) the single thread fiber number is below the 1.5dtex,
The (ii) ratio A of the area A of core and the area B of sheath portion: B is 5: 95~80: 20 a scope,
(iii) single end strength is more than the 3.0cN/dtex,
(iv) the frictional electrification voltage of yarn is below the 2000V,
(v) polyester A is an antistatic polyester, in this antistatic polyester, with respect to aromatic polyester 100 weight portions, contain represented poly (oxyalkylene) base system polyethers 0.2~30 weight portion of (a) following general formula (1) and (b) be essentially non-reacted organic ion compound 0.05~10 weight portion as antistatic additive with this polyester
R 2O-(CH 2CH 2O)n(R 1O)m-R 2?(1)
[in the formula, R 1Be alkylidene or the substituted alkylene of carbon number more than 2, R 2Be the monovalence alkyl of hydrogen atom, carbon number 1~40, the monovalence hydroxyl hydrocarbon of carbon number 2~40 or the monovalence acyl group of carbon number 2~40, n is the integer more than 1, and m is the integer more than 1]
Here, copolyester B is preferably:
Copolymerization with respect to the polyester gross weight be the organic system ultraviolet radiation absorption composition of 0.1~5.0 weight % polyester,
Copolymerization with respect to all acid composition except that metal organic sulfonate be 1.0~5.0 moles of % metal organic sulfonate polyester or
Copolymerization convert with phosphorus atoms with respect to the polyester gross weight and count 1,000~10, the polyester of the phosphorus flame retardant composition that the following general formula (2) of 000ppm is represented
[changing 1]
[in the above-mentioned formula, R 1Be the hydroxy alkyl of hydrogen or carbon number 1~10, R 2Be the alkyl of hydrogen, carbon number 1~10 or the aryl of carbon number 6~24, R 3Alkyl or hydroxy alkyl for hydrogen, carbon number 1~10].
In addition, above-mentioned antistatic behaviour core-sheath-type polyester superfine fibre is preferred: in the cross section vertical, have 3~8 fins from the outstanding laterally shape of fibre section central part with the single thread length direction, or with the vertical cross section of single thread length direction in have the flat pattern that has vertically engaged 3~6 circular section single thread along it.
In addition, according to the present invention, provide:
(2) antistatic polyester composit false twisting processing yarn, its be 2 kinds of different polyester filament yarns of percentage elongation alternatively formed in the vertical the boundling portion that comprises mutual twist yarn shape coiling portion and the portion that interweaves, with open the polyester composit false twisting processing yarn that fine portion forms, it is characterized in that, satisfy the important document of following (i)~(iv)
(i) the polyester filament yarn X that percentage elongation is little is the core-sheath-type polyester complex fiber that core is made of copolyester B polyester A, sheath portion, and polyester A comprises antistatic polyester, in this antistatic polyester, with respect to aromatic polyester 100 weight portions, contain represented poly (oxyalkylene) base system polyethers 0.2~30 weight portion of (a) following general formula (1) and (b) be essentially non-reacted organic ion compound 0.05~10 weight portion as antistatic additive with this polyester
The polyester filament yarn Y that (ii) percentage elongation is big comprises polyester, and it is the delustering agent of 0~10wt% that this polyester contains with respect to aromatic polyester 100 weight portions,
(iii) be 2 layers of structure, wherein, polyester filament yarn X constitutes the core of composit false twisting yarn, and polyester filament yarn Y will batch around the core to mutual twist yarn shape constitutes outer portion (sheath portion),
(iv) the average yarn length of polyester filament yarn Y is longer by 5~20% than the average yarn of polyester filament yarn X,
R 2O-(CH 2CH 2O)n(R 1O)m-R 2?(1)
[in the formula, R 1Be alkylidene or the substituted alkylene of carbon number more than 2, R 2Be the monovalence alkyl of hydrogen atom, carbon number 1~40, the monovalence hydroxyl hydrocarbon of carbon number 2~40 or the monovalence acyl group of carbon number 2~40, n is the integer more than 1, and m is the integer more than 1];
(3) antistatic polyester mixes and to knit yarn, it is characterized in that, comprise antistatic polyester filament yarn X, with polyester filament yarn Y, and satisfy following (i)~(condition vi),
(i) antistatic polyester filament yarn X is the core-sheath-type polyester complex fiber that core is made of copolyester B polyester A, sheath portion, and polyester A comprises antistatic polyester, in this antistatic polyester, with respect to aromatic polyester 100 weight portions, contain represented poly (oxyalkylene) base system polyethers 0.2~30 weight portion of (a) following general formula (1) and (b) be essentially non-reacted organic ion compound 0.05~10 weight portion as antistatic additive with this polyester
(ii) the single thread fiber number of polyester filament yarn X is below the 1.5dtex,
(iii) mixing the frictional electrification voltage of knitting yarn is below the 2000V,
(iv) mix knit yarn be successively via air interweave operation, lax heat treatment step and,
(v) the mixed ratio of knitting of polyester filament yarn X and polyester filament yarn Y is 8: 2~6: 4,
(vi) polyester filament yarn X constitutes outer portion, the polyester filament yarn Y formation internal layer portion of knitting yarn of mixing,
R 2O-(CH 2CH 2O)n(R 1O)m-R 2?(1)
[in the formula, R 1Be alkylidene or the substituted alkylene of carbon number more than 2, R 2Be the monovalence alkyl of hydrogen atom, carbon number 1~40, the monovalence hydroxyl hydrocarbon of carbon number 2~40 or the monovalence acyl group of carbon number 2~40, n is the integer more than 1, and m is the integer more than 1]
(4) antistatic polyester mixes the manufacture method of knitting yarn, it is characterized in that, with percentage elongation (ELA) is more than 80%, elastic recovery rate (ERA) during 10% stretching is below 50%, stretching modulus of rigidity (EMA) is below the 5.89GPa, crystallization degree (XpA) is more than 25%, boiling water shrinkage (BWSA) is below 3%, thermal stress under 160 ℃ (TSA) is below the 0.44mN/dtex, and satisfy following (i)~the antistatic polyester filament yarn X ' of important document relax after the heat treatment, be below 40% with percentage elongation (ELB) again, stretching modulus of rigidity (EMB) is more than the 7.85GPa, boiling water shrinkage (BWSB) is more than 5%, thermal stress under 160 ℃ (TSB) is carried out doubling for the above polyester filament yarn Y ' of 0.88mN/dtex, so that the weight ratio of polyester mutifilament yarn X ' and polyester mutifilament yarn Y ' is 45/55~70/30, carry out interleaving treatment then
(i) the core-sheath-type polyester complex fiber that constitutes by copolyester B by polyester A, sheath portion for core of antistatic polyester multifilament textile X ', and polyester A comprises antistatic polyester, in this antistatic polyester, with respect to aromatic polyester 100 weight portions, contain represented poly (oxyalkylene) base system polyethers 0.2~30 weight portion of (a) following general formula (1) and (b) be essentially non-reacted organic ion compound 0.05~10 weight portion as antistatic additive with this polyester
(ii) the single thread fiber number of polyester mutifilament yarn X ' is below the 1.5dtex,
R 2O-(CH 2CH 2O)n(R 1O)m-R 2?(1)
[in the formula, R 1Be alkylidene or the substituted alkylene of carbon number more than 2, R 2Be the monovalence alkyl of hydrogen atom, carbon number 1~40, the monovalence hydroxyl hydrocarbon of carbon number 2~40 or the monovalence acyl group of carbon number 2~40, n is the integer more than 1, and m is the integer more than 1].
Summary of the invention
According to the present invention, provide the polyester superfine fibre with antistatic behaviour and the manufacture method thereof of excellent in te pins of durability.
In addition, according to the present invention, provide can by import to above-mentioned antistatic polyester superfine fibre the 3rd composition or with compoundization of other fiber, the change of cross sectional shape etc., and give the flexible touch on fluffy sense, surface of ultraviolet screening effect, cation dyeable, anti-flammability, spinning sample and elasticity, resilience, dry feeling, naturally sense and Si Bennaizi Texturized (ス パ Na イ ズ) outward appearance, imitate the antistatic polyester superfine fibre and the manufacture method thereof of various functions such as wool sense of touch, fold are restorative, water-absorbing fast-drying.
Description of drawings
The sketch of one example of the false twisting processing unit (plant) that uses among [Fig. 1] expression the present invention.
The schematic diagram of one example of the knot structure of [Fig. 2] expression antistatic polyester composit false twisting processing yarn of the present invention
[Fig. 3] expression antistatic polyester of the present invention mixes knits the mixed sketch of knitting an example of device that uses in the manufacturing of yarn.
[Fig. 4] expression contains the oblique view that the mixed fold of knitting the cloth and silk of yarn of antistatic polyester of the present invention is recovered the general survey of determinator.
The ideograph of one example in the cross section of [Fig. 5] expression antistatic behaviour core-sheath-type polyester superfine fibre of the present invention.
The ideograph of one example of the spinning nozzle tap that uses when [Fig. 6] expression is carried out spinning to the antistatic behaviour core-sheath-type polyester superfine fibre of Fig. 5.
The ideograph of one example in the cross section of [Fig. 7] expression flat cross section fiber of the present invention.
[Fig. 8] expression is of the present invention, engaged the ideograph of an example in the flat pattern cross section of 3~6 circular section single thread in the vertical.
Symbol description
Among Fig. 1,3, the interweave air nozzle, 8 of usefulness of mutually different 2 strands, 4 expression thread-carriers, 5 expression tension adjusting devices, 6 expression feed rollers, 7 expressions of 3 ' expression percentage elongation represents that the 1st outlet roller, 9 represents that heater, 10 represents that false twisting instrument, 11 represents the 2nd outlet roller, in addition, 13 expression cheeses;
Among Fig. 2, I represents that mutual twist yarn shape coiling portion, II represent that the portion of interweaving, III represent out fine portion;
Among Fig. 3, X ' expression by implementing lax heat treatment interweave nozzle, 4 expressions the 2nd carry-over pinch rolls, 5 expression noncontact heaters, 6 of polyester filament yarn, Y ' expression polyester filament yarn, 1 expression donor rollers, 2 expression the 1st carry-over pinch rolls (warm-up mill), 3 expressions of spontaneous stretching represent packages;
Among Fig. 5, a1 represents from length, the b1 on inscribed circle center to the fin summit of fibre section inner surface: the inscribe radius of a circle (core extrapolation inscribed circle) of expression fibre section inner surface;
Among Fig. 6, a2 represents that core forms central point to fin that the radius, the b2 that portal with circular row represent that circular row is portalled and forms length with the leading section of tap;
Among Fig. 8, A represents the maximum of the maximum of the length on long limit, length that B represents minor face, the minimum of a value of length that C represents minor face.
The specific embodiment
Below the application's the 1st working of an invention mode is elaborated.
The application the 1st invention is an antistatic behaviour core-sheath-type polyester superfine fibre, its be core by polyester A, sheath portion by the core-sheath-type polyester complex fiber that copolyester B constitutes, it is characterized in that, satisfy following important document,
(i) the single thread fiber number is below the 1.5dtex,
The (ii) ratio A of the area A of core and the area B of sheath portion: B is 5: 95~80: 20 a scope,
(iii) single end strength is more than the 3.0cN/dtex,
(iv) the frictional electrification voltage of yarn is below the 2000V,
(v) polyester A is an antistatic polyester, in this antistatic polyester, with respect to aromatic polyester 100 weight portions, contain represented poly (oxyalkylene) base system polyethers 0.2~30 weight portion of (a) following general formula (1) and (b) be essentially non-reacted organic ion compound 0.05~10 weight portion as antistatic additive with this polyester
R 2O-(CH 2CH 2O)n(R 1O)m-R 2?(1)
[in the formula, R 1Be alkylidene or the substituted alkylene of carbon number more than 2, R 2Be the monovalence alkyl of hydrogen atom, carbon number 1~40, the monovalence hydroxyl hydrocarbon of carbon number 2~40 or the monovalence acyl group of carbon number 2~40, n is the integer more than 1, and m is the integer more than 1].
Said polyester is with by dicarboxylic acids or its ester formation property derivative among the present invention, with be selected from glycol or its ester form property derivative, hydroxycarboxylic acid or its ester form in property derivative, the lactone to carry out polymer or copolymer that polycondensation forms more than a kind be object, preferred illustration has the aromatic polyester of aromatic rings as the chain element of polymer.
As said two functionality aromatic carboxylic acids here, can enumerate terephthalic acid (TPA), M-phthalic acid, phthalic acid, 1, the 5-naphthalenedicarboxylic acid, 2, the 5-naphthalenedicarboxylic acid, 2, the 6-naphthalenedicarboxylic acid, 4,4 '-biphenyl dicarboxylic acid, 3,3 '-biphenyl dicarboxylic acid, 4,4 '-the diphenyl ether dioctyl phthalate, 4,4 '-the diphenyl methane dioctyl phthalate, 4,4 '-the diphenyl sulfone dioctyl phthalate, 4,4 '-diphenyl isopropylidene dioctyl phthalate, 1, two (phenoxy group) ethane-4,4 of 2-'-dioctyl phthalate, 2,5-anthracene dioctyl phthalate, 2,6-anthracene dioctyl phthalate, 4,4 '-to the phenylene dioctyl phthalate, 2, the 5-pyridinedicarboxylic acid, the beta-hydroxy ethoxybenzoic acid, P-hydroxybenzoic acid etc., preferred especially terephthalic acid (TPA).
These two functionalities aromatic carboxylic acids can also more than 2 kinds and be used.Should illustrate, if a small amount of, these two functionalities aromatic carboxylic acids simultaneously also can and with as two functionality aliphatic carboxylic acids of adipic acid, azelaic acid, decanedioic acid, dodecanedioic acid, as two functionality alicyclic carboxylic acids of cyclohexane cyclohexanedimethanodibasic, M-phthalic acid 5-sodium sulfonate etc. more than a kind or 2 kinds and usefulness.
In addition, as diol compound, preferably can enumerate as ethylene glycol, propylene glycol, butanediol, hexylene glycol, neopentyl glycol, 2-methyl isophthalic acid the aliphatic diol of ammediol, diethylene glycol (DEG), trimethylene, as alicyclic diol of 1,4 cyclohexane dimethanol etc. and their mixture etc.In addition, if a small amount of, these diol compounds simultaneously can also copolymerization two terminal or single terminal untight polyether polyols.
And then, be the scope of wire substantially at polyester, can use polycarboxylic acid, as the polyalcohol of glycerine, trimethylolpropane, pentaerythrite as trimellitic acid, pyromellitic acid.
In addition, as above-mentioned hydroxycarboxylic acid, can enumerate the acid of glycollic acid, lactic acid, hydracrylic acid, hydroxybutyric acid, hydroxypentanoic acid, hydroxyl, hydroxybenzoic acid, P-hydroxybenzoic acid, 6-hydroxyl-2-naphthoic acid and their ester formation property derivative etc.As above-mentioned lactone, can enumerate caprolactone, valerolactone, propiolactone, hendecane lactone, 1,5-oxepane-2-ketone etc.
As concrete optimization aromatic polyester, can enumerate polyethylene terephthalate, polybutylene terephthalate (PBT), poly terephthalic acid hexylene glycol ester, PEN, PBN, poly-ethylidene-1, two (phenoxy group) ethane-4 of 2-, 4 '-dicarboxylic acid esters etc., and as the copolyester of polyethylene glycol isophthalate terephthalate, polybutylene terephthalate (PBT) isophthalic acid ester, polybutylene terephthalate (PBT) decane dicarboxylic acid esters etc.Wherein, the polyethylene terephthalate and the polybutylene terephthalate (PBT) of the balance of engineering properties, formability etc. have especially preferably been obtained.
As aliphatic polyester resin, but illustration with the aliphatic hydroxyl carboxylic acid be the main composition composition polymer, to form property derivative and aliphatic polyol with aliphatic polybasic carboxylic acid or its ester be that principal component is carried out polymer that polycondensation forms or their copolymer.
As being the polymer of main composition composition with the aliphatic hydroxyl carboxylic acid, but illustration glycollic acid, lactic acid, hydracrylic acid, hydroxybutyric acid, hydroxypentanoic acid, hydroxyl be the condensation polymer of acid etc. or copolymer etc., wherein, can enumerate polyglycolic acid, PLA, poly-3-hydroxyl carboxylic butyric acid, poly-4-poly butyric, poly-3-hydroxycaproic acid or polycaprolactone and their copolymer etc., stereoscopic composite PLA, the poly-dl-lactide that can use poly (l-lactic acid), poly-D-lactic acid especially aptly and form the stereoscopic composite crystallization.
As PLA, can use with L-lactic acid and/or D-lactic acid is the PLA of main repetitive, and preferred especially fusing point is the PLA more than 150 ℃ (mainly meaning this composition here, accounts for all more than 50%).When fusing point is lower than 150 ℃, take place between single thread when forming fiber fusion cause draftability bad, produce when dyeing adds man-hour, heat setting, during the friction heating fusion shortcoming etc., since product quality significantly reduce, so be not preferred for the dress material purposes.
The fusing point of preferred PLA is more than 170 ℃, and further preferred fusing point is more than 200 ℃.Here, fusing point means the peak temperature that utilizes DSC to measure the melting peak of gained.In order to give heat resistance, preferred PLA forms the stereoscopic composite crystallization especially.
Here, the stereoscopic composite PLA is meant the eutectic that poly-L-lactic acid fragment and poly-D lactic acid fragment form.
The stereoscopic composite crystallization is usually than poly-L-lactic acid or the independent crystalline melt point height that forms of poly-D lactic acid, thereby contain a little and can expect to improve stable on heating effect, particularly the amount of stereoscopic composite crystallization with respect to all crystallization contents for for a long time, this effect is brought into play significantly.For stereoscopic composite crystallization degree (S) according to following formula, preferred more than 95%, further preferred 100%,
S=[ΔHms/(ΔHmh+ΔHms)] × 100
(wherein, Δ Hms be the crystallization of stereoscopic composite phase melt enthalpy, Δ Hmh is the enthalpy that melts of homogeneous phase PLA crystallization).
Above-mentioned aromatic polyester synthesizes by any means.For example, if describe at polyethylene terephthalate, then can directly carry out esterification, make as the lower alkyl esters of the terephthalic acid (TPA) of terephthalic acid (TPA) dimethyl esters and ethylene glycol and carry out ester exchange reaction or make terephthalic acid (TPA) and oxirane reacts by making terephthalic acid (TPA) and ethylene glycol, and generate the glycol ester of terephthalic acid (TPA) and/or its oligomer the 1st section reaction, then this product is under reduced pressure heated, carry out polycondensation reaction until the 2nd section reaction of the degree of polymerization of expectation and manufacturing easily.
Among the present invention, be matched with the poly (oxyalkylene) base system polyethers (a) among the polyester A of core so long as be insoluble getting final product substantially in polyester, it can be the polyether polyols that comprises single alkylidene oxide unit, it also can be the copolymerization polyether polyols that comprises alkylidene oxide unit more than two kinds, in addition, can also be that the represented polyoxyethylene of following general formula (I) is a polyethers
R 2O-(CH 2CH 2O)n(R 1O)m-R 2?(1)
[in the formula, R 1Be alkylidene or the substituted alkylene of carbon number more than 2, R 2Be the monovalence alkyl of hydrogen atom, carbon number 1~40, the monovalence hydroxyl hydrocarbon of carbon number 2~40 or the monovalence acyl group of carbon number 2~40, n is the integer more than 1, and m is the integer more than 1].
Concrete example as described poly (oxyalkylene) base system polyethers, can enumerate molecular weight and be the polyoxyethylene glycol more than 4000, molecular weight is the polyoxy propylene glycol more than 1000, the polyoxy tetramethylene glycol, molecular weight is the oxirane more than 2000, epoxy propane copolymer, the trimethylolpropane ethylene oxide adduct of molecular weight more than 4000, the nonyl phenol ethylene oxide adduct of molecular weight more than 3000, and on their the terminal OH base addition carbon number be the compound of the substituted epoxy ethane more than 6, wherein, preferred molecular weight is 10000~100000 polyoxyethylene glycol, with molecular weight be 5000~16000 polyoxyethylene glycol two terminal go up additions carbon number be the compound of 8~40 alkyl substituted epoxy ethane.
The use level of described poly (oxyalkylene) base system polyether compound is the scope of 0.2~30 weight portion with respect to aforementioned aromatic polyester 100 weight portions.Hydrophily deficiency then during less than 0.2 weight portion can't present sufficient antistatic behaviour.On the other hand, do not see the raising effect of initial antistatic behaviour than 30 weight portions yet, can damage the engineering properties of resulting composition on the contrary, and this polyethers easy seepage that becomes, thus during melt-shaping tablet to the deterioration that also becomes of the reduction of nipping property, the shape stability of extruder.
Among the present invention, cooperate organic ionic compound for the antistatic behaviour that improves polyester A especially.As the organic ion compound, as preferably, can enumerate metal organic sulfonate shown in for example following general formula (II), (III) and sulfonic acid quaternary alkylphosphonium salt,
RSO 3M      (II)
(in the formula, R represents that the alkyl of carbon number 3~30 or aryl, the M of carbon number 7~40 represent alkali metal or alkaline-earth metal)
RSO 3PR 1R 2R 3R 4      (III)
(in the formula, R is the alkyl of carbon number 3~30 or the aryl of carbon number 7~40, R 1, R 2, R 3And R 4Be alkyl or aryl and wherein preferred low alkyl group, phenyl or benzyl).
In the above-mentioned formula (II), when R was alkyl, alkyl can be the straight chain shape or also can have branched building block.M is Na, K, and alkali metal or Mg such as Li, alkaline-earth metals such as Ca, wherein, preferred Li, Na, K.The only a kind of use separately of described metal organic sulfonate also can mix more than 2 kinds and use.As preferred concrete example, can enumerate sodium alkyl sulfonate mixture, neopelex mixture, neopelex (gravity die, soft type), DBSA lithium (gravity die, soft type), magnesium dodecyl benzene sulfonate (gravity die, soft type) of the average out to 14 of octadecyl sodium sulfonate, sodium octyl, dodecyl sodium sulfate, carbon number etc.
In addition, only a kind of use separately of the sulfonic acid quaternary alkylphosphonium salt in the formula (III) also can mix more than 2 kinds and use.As preferred concrete example, the alkyl sulfonic acid Ding of the alkyl sulfonic acid tetraphenylphosphoniphenolate of the alkyl sulfonic acid 4-butyl-phosphonium of the average out to 14 of carbon number, the average out to 14 of carbon number, the average out to 14 of carbon number base triphenyl phosphonium, DBSA 4-butyl-phosphonium (gravity die, soft type), DBSA tetraphenylphosphoniphenolate (gravity die, soft type), DBSA Bian base triphenyl phosphonium (gravity die, soft type) etc.
Described organic ionic compound can use a kind, also can be more than 2 kind and usefulness, and its use level is preferably the scope of 0.05~10 weight portion with respect to aromatic polyester 100 weight portions.Then the effect that improves of antistatic behaviour is little less than 0.05 weight portion, surpass the engineering properties that 10 weight portions then can damage composition, the deterioration that also becomes of this ionic compound easy seepage that also becomes, thereby nipping property of the extruder reduction of the tablet during melt-shaping, shape stability.
Among the present invention, for fiber is given various functions with the polyester B of sheath portion as copolyester.Here, copolymerization is that the 3rd composition is integrated in the polymer backbone by common polymerisation, is also contained in blend back in polymer in addition and is integrated into the polymeric species of chain extension agent in the polymer backbone, so-called with end group reaction or is integrated into polymeric species in the polymer backbone in redistribution reaction.
At first, among the present invention, in order to improve weather fastness, with respect to polyester B, preferably containing with respect to the polyester gross weight is preferred 0.5~3.0 weight % of 0.1~5.0 weight %() the organic system ultra-violet absorber carry out copolymerization.The content of organic system ultra-violet absorber then can not get sufficient UV absorbing properties than 0.1 weight % hour, so not preferred.On the contrary, when the content of organic system ultra-violet absorber is bigger than 5.0 weight %, will contain the polyester spinning of organic system ultra-violet absorber and when obtaining polyester fiber, the process stability of spinning suffers damage, the distinctiveness of color also reduces, so not preferred.
As the organic system ultra-violet absorber, but the illustration benzo
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Piperazine is that organic uv absorbers, benzophenone series organic uv absorbers, benzotriazole are that organic uv absorbers, salicylic acid are organic uv absorbers etc.Wherein, aspect Undec in the spinning stage, preferred especially benzo
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Piperazine is an organic uv absorbers.Benzo
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Piperazine is that the excellent especially reason of organic uv absorbers is not clear, but compares with other ultra-violet absorber, can enumerate high-fire resistance, with based on the compatibility of the polyester of cyclic imide ester well so seepage is few etc.
As described benzo
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Piperazine is an organic uv absorbers, aptly illustration Japanese kokai publication sho 62-11744 communique disclosed those.That is, 2-methyl-3,1-benzo
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Piperazine-4-ketone, 2-butyl-3, the 1-benzo
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Piperazine-4-ketone, 2-phenyl-3, the 1-benzo
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Piperazine-4-ketone, 2, and 2 '-ethylenebis (3, the 1-benzo Piperazine-4-ketone), 2,2 '-tetramethylene two (3, the 1-benzo Piperazine-4-ketone), 2,2 '-TOPOT 2,2 (3, the 1-benzo
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Piperazine-4-ketone), 1,3,5-three (3, the 1-benzo
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Piperazine-4-ketone-2-yl) benzene, 1,3, and 5-three (3, the 1-benzo
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Piperazine-4-ketone-2-yl) naphthalene etc.
In addition, form in the polyester of antistatic behaviour core-sheath-type polyester superfine fibre of the present invention, the ultraviolet radiation absorption of inorganic system and/or reflective agent preferably contain below the 0.5 weight %.
When the ultraviolet radiation absorption of inorganic system and/or the content of reflective agent were bigger than 0.5 weight %, then not only impaired but also the knitting or woven property of distinctiveness was also impaired, so not preferred.Should illustrate,, can enumerate inorganic compounds such as titanium dioxide, zinc oxide, aluminium oxide, magnesia, talcum, kaolin, calcium carbonate, sodium carbonate as the ultraviolet radiation absorption and/or the reflective agent of described inorganic system.
Should illustrate, form in the polyester of antistatic behaviour core-sheath-type polyester superfine fibre of the present invention, except the organic system ultra-violet absorber, in the scope of not damaging purpose of the present invention, also can add pore former, cationic-dyeable agent, painted more than a kind or 2 kinds of agent, heat stabilizer, fire retardant, fluorescent whitening agent, colouring agent, antistatic agent, hygroscopic agent, antiseptic, anion propellant etc. that prevents as required.
And then core polyester A need be 5: 95~80: 20 scope with the copolyester B's of sheath portion perpendicular to the ratio of the area in the cross section of fiber axis.The area ratio was less than 5: 95 o'clock, then the performance of the antistatic property that is got by polyester A becomes insufficient, greater than 80: 20 o'clock, then when the alkali decrement of implementing more than 10%, the antistatic polyester meeting stripping of core, antistatic property descended, the intensity of stretch yarn reduces simultaneously, therefore become below the 3.0cN/dtex, the undercapacity when being made as cloth and silk is unsuitable for the purposes of desired strengths such as motion dress material, purposes is restricted, so not preferred.
In the antistatic behaviour core-sheath-type polyester superfine fibre of the present invention, use present known compined spinning apparatus, use aforementioned copolyester B, use polyester A in the sheath side at core, carry out melt spinning with the speed that 2000~3000m/ divides, and the ratio (below be designated as draw ratio) of the velocity of discharge and hauling speed when spinning is drawn in 100~800 scope is important.
As the method for heat-treating, can adopt with above-mentioned speed and carry out melt spinning, when stretching or the method for carrying out afterwards etc., throwing condition arbitrarily.
In addition, after spinning, can implement so-called DTY processing to gained antistatic behaviour core-sheath-type polyester superfine fibre, or also can stretch temporarily batch after, implement false twisting processing.
Among the present invention, also preferably woven the and knit goods of yarn or this fiber manufacturing being heat-treated in the temperature more than 100 ℃, is the suitable arrangementization due to the migration of polyethers and contained as required various additives with contained polyoxyethylene in the stabilisation that promotes structure and the fiber.And then also can and use lax heat treatment etc. as required.
In addition as required, also can implement to process after the suitable hydrophiling, and to do like this be preferred to antistatic behaviour core-sheath-type polyester superfine fibre of the present invention or by the woven and knit goods of this fiber manufacturing.As processing after this hydrophiling, preferably for example can adopt, the method of handling with the aqueous liquid dispersion of the polyester polyether block copolymer that comprises terephthalic acid (TPA) and/or M-phthalic acid or their lower alkyl esters, low-grade alkylidene glycol and poly alkylene glycol, or hydrophilic monomers such as acrylic acid, methacrylic acid are carried out glycerol polymerization, then with method of its sodium saltization etc.
In addition, among the present invention,, with respect to all acid composition the sour composition that contains azochlorosulfonate acid alkali of 1.0~5.0 moles of % preferably with respect to polyester B copolymerization in order to improve dyeability.The copolymerization amount of sour composition that contains azochlorosulfonate acid alkali can not get sufficient dyeability during less than 0.5 mole of %, can't have stainability to cation dyes, when surpassing 5.0 moles of %, the melt viscosity of mylar uprises, and can cause the deterioration of spinning operation or the reduction of yarn intensity, so not preferred.
Above-mentionedly contain the sour composition of azochlorosulfonate acid alkali so long as the composition that contains azochlorosulfonate acid alkali that has with the functional group of pet reaction gets final product, be not particularly limited, as an example, can enumerate M-phthalic acid 5-sodium sulfonate, M-phthalic acid 5-potassium sulfonate, M-phthalic acid 5-sulfonic acid lithium, naphthalenedicarboxylic acid sodium sulfonate, terephthalic acid (TPA) 5-sodium sulfonate etc.Wherein, particularly color emissivity and the spinnability due to the cation dyes of M-phthalic acid 5-sodium sulfonate is good, so suitable.
In addition, constitute among the polyester B of fiber of the present invention, preferably contain, preferred especially copolymerization has the represented organic phosphorus compound of following general formula (2) as fire retardant, so that with respect to the polyester gross weight, count 1,000~10 with phosphorus atoms content, 000ppm is preferably 3,000~9,000ppm
[changing 2]
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[in the above-mentioned formula, R 1Be the hydroxy alkyl of hydrogen or carbon number 1~10, R 2Be the alkyl of hydrogen, carbon number 1~10 or the aryl of carbon number 6~24, R 3Alkyl or hydroxy alkyl for hydrogen, carbon number 1~10].
Especially, when containing the above-mentioned composition that contains azochlorosulfonate acid alkali among the polyester B, melt viscosity is difficult to cause that fusion drops during than common polyester fiber height, burning, so there is the shortcoming of easy fire spreading, produces effect so bring into play containing of fire retardant fully.
The content of above-mentioned organic phosphorus compound in the content of phosphorus atoms, less than 1, then can not get sufficient fire resistance during 000ppm, surpass 10, and during 000ppm, so then spinning operation reduction or yarn intensity deficiency be not preferred.
Then, the application's the 2nd working of an invention mode is elaborated.
The application's the 2nd invention is an antistatic polyester composit false twisting processing yarn, its be 2 kinds of different polyester filament yarns of percentage elongation alternatively formed in the vertical the boundling portion that comprises mutual twist yarn shape coiling portion and the portion that interweaves, with open the polyester composit false twisting processing yarn that fine portion forms, it is characterized in that, satisfy the important document of following (i)~(iv):
(i) the polyester filament yarn X that percentage elongation is little is the core-sheath-type polyester complex fiber that core is made of copolyester B polyester A, sheath portion, and polyester A comprises antistatic polyester, in this antistatic polyester, with respect to aromatic polyester 100 weight portions, contain represented poly (oxyalkylene) base system polyethers 0.2~30 weight portion of (a) following general formula (1) and (b) be essentially non-reacted organic ion compound 0.05~10 weight portion as antistatic additive with this polyester
The polyester filament yarn Y that (ii) percentage elongation is big comprises polyester, and it is the delustering agent of 0~10wt% that this polyester contains with respect to aromatic polyester 100 weight portions,
(iii) be 2 layers of structure, wherein, polyester filament yarn X constitutes the core of composit false twisting yarn, and polyester filament yarn Y will batch around the core to mutual twist yarn shape constitutes outer portion (sheath portion),
(iv) the average yarn length of polyester filament yarn Y is longer by 5~20% than the average yarn of polyester filament yarn X,
R 2O-(CH 2CH 2O)n(R 1O)m-R 2?(1)
[in the formula, R 1Be alkylidene or the substituted alkylene of carbon number more than 2, R 2Be the monovalence alkyl of hydrogen atom, carbon number 1~40, the monovalence hydroxyl hydrocarbon of carbon number 2~40 or the monovalence acyl group of carbon number 2~40, n is the integer more than 1, and m is the integer more than 1].
Polyester filament yarn X core, that percentage elongation is little that constitutes antistatic polyester composit false twisting processing yarn of the present invention is the core-sheath-type polyester complex fiber that core is made of copolyester B polyester A, sheath portion, the identical polyester of polyester A, B that uses in the core-sheath-type composite fibre that this polyester A, B are with the application the 1st invents.
Then, constituting the big polyester filament yarn Y of the percentage elongation of antistatic polyester composit false twisting processing yarn of the present invention will be that the polyester filament of main repetitive is as main object with ethylene glycol terephthalate, trimethylene terephthalate or tetramethylene terephthalate, but as required also can be for (being benchmark with whole repetitives usually on a small quantity, be that 15 moles of % are following, preferred 10 moles of % following, preferred especially 5 moles of % are following) copolymerization the copolyester of the 3rd composition, in addition, can also add delustering agent, other additive.
Wherein, by carrying out the alkali decrement treatment, and when fiber surface or fibrous inside contain the pore former that forms micropore or fine ditch, by the shape of this hole or ditch, can embody various effects such as water imbibition, natural thin,tough silk sample quality, distinctiveness, dry and comfortable sense of touch, so preferred.
As the method that obtains antistatic polyester composit false twisting processing yarn of the present invention, can interweave simultaneously, twist by not stretch yarn, and it is carried out backtwisting form mutual coiling yarn and obtain above-mentioned polyester filament yarn X and polyester filament yarn Y.
As the combination of the polyester filament yarn more than 2 kinds among the present invention, use can further stretch strand more than 40% of the strand littler than this percentage elongation but preferably use draw false twisting to the strand more than at least 1.2 times to be used as the little strand of percentage elongation and the big strand of percentage elongation.
Should illustrate, the percentage elongation of the polyester filament yarn X that percentage elongation is little is more than 50%, preferred be suitable more than 60%, the percentage elongation of the polyester filament yarn Y that percentage elongation is big is preferably more than 100%, and the elongation rate variance of low elongation polyester filament yarn X and high elongation rate polyester filament yarn Y is more than 20%, be preferably more than 40%, more preferably more than 50%.More preferably 50~70%.
Here, if the elongation rate variance then can not get the bulkiness of false-twisted yarn, so not preferred less than 20%.Here, when regulating the percentage elongation of polyester filament yarn X, polyester filament yarn Y, can be undertaken, preferably stretching ratio etc. be regulated by known method.
In addition, the ratio of polyester filament yarn X and polyester filament yarn Y can suit to select to set according to purpose, but preferably respectively does for oneself more than 20% both usage ratio preferred polyester yarn filament yarn X: polyester filament yarn Y=25: 75~75: 25(weight).The ratio of the polyester filament yarn Y that preferred especially percentage elongation is big is many, in the time of in the ratio of (polyester filament yarn X)/(polyester filament yarn Y), and 30/70~45/55 scope that suitable is.
By taking as above-mentioned formation, polyester filament yarn Y can preferentially be stretched in the composit false twisting operation, make that the infringement of polyester filament yarn X is few, the generation of broken yarn, fluffing is few, in addition, even polyester filament yarn X fluffs, also owing to be covered, so can alleviate problem in the following cloth and silk chemical industry preface by polyester filament yarn Y.
And then, in the scope of not damaging purpose of the present invention, also can compound other fiber, for example metal coated fibers or carbon particle are sneaked into fiber and are given electric conductivity, but and during with other fiber, its ratio is not if be below 30% of integral body, then bulkiness has the tendency of reduction, so not preferred.
Among the present invention, preferably that percentage elongation is different 2 kinds or the not stretch yarn more than it draws together, implement the air interleaving treatment by air nozzle before stretching.Injection method as air, can adopt in the method for spraying with the rectangular direction of the yarn of advancing, follow any means of method that the preceding line direction of yarn into sprays etc., but can obtain the comparatively excellent product of gloss, can obtain the softer product of quality by the former, thereby can select according to purpose is suitable by the latter.Yet, in this interleaving treatment, if make over feed rate(OFR) excessive, the process stability in the time of can producing the manufacturing of coil (loop) infringement cloth and silk in a large number, thereby expectation is below 10%.
In addition, what percentage elongation was different can not be provided with the overfeeding rate variance between stretch yarn, but this moment is excessive as if making difference, and then coil can produce in a large number, thereby adopts identical over feed rate(OFR) usually.
False-twisting device can be used winding twirling or rotating of the acupuncture needle in adding spindle, fluid-type air false twisting nozzle, internal connecting type or the circumscribed friction false twist device on (twist pin), any device in the band friction assembly.
By Fig. 1 this embodiment is described, mutually different 2 strands 3,3 ' of percentage elongation carry out doubling at thread-carrier 4, be supplied to the air nozzle 7 of the usefulness that interweaves then via tension adjusting device 5, feed roller 6, form interlaced yarns here with the above intertwined point of 13/m.Then, this interlaced yarns is supplied to the draw false twisting district by the 1st outlet roller 8, via heater 9, false twisting instrument 10, after the traction of the 2nd outlet roller 11, batches and is cheese 13.
Here, give interweave the back heat-treat with heater while applying overfeeding, polyester filament yarn Y can shrink, polyester filament yarn X shrinks hardly or self takes place and upholds, produce yarn length poor (the yarn foot is poor) between polyester filament yarn X and the polyester filament yarn Y, this when making cloth and silk fluffy, like staple fiber yam is relevant.
Use accompanying drawing to describe for antistatic polyester composit false twisting processing yarn of the present invention.Fig. 2 is the side view of false-twisted yarn of the present invention.Among Fig. 2, I represents that mutual twist yarn shape coiling portion, II represent that the portion of interweaving, III represent out fine portion.
In the antistatic polyester composit false twisting processing yarn of the present invention, importantly, as Fig. 2 institute, be formed with alternately in the vertical and comprise the mutual twist yarn shape coiling portion (I) and the boundling portion (X) of portion (II) that interweaves, and open fine portion (III).
In the boundling portion of the present invention (X), mutual twist yarn shape coiling portion (I) be mainly comprise polyester filament yarn Y outer portion basically with the reeling part of the core that mainly comprises polyester filament yarn X of boundling state.In addition, the portion that interweaves (II) is that aforementioned polyester filament yarn X and polyester filament yarn Y knit the part that state closely is shot through with to mix, below, will (I) among the present invention and (II) be generically and collectively referred to as boundling portion (X).
In such boundling portion (X), the portion that interweaves (II) whole strands of having tied tight so the cross section second moment is big, can be given high resilience to the cloth and silk that finally obtains.
On the other hand, mutual twist yarn shape coiling portion (I) compares with the portion of interweaving (II) to have the part of expanding, and can present elastic force to extruding, can give quality such as tension force, elasticity to cloth and silk.
Relative therewith, it is adjacent with aforementioned boundling portion (X) that to open fine portion (III) be following part, wherein, mainly the part of the core that is made of polyester yarn A mainly is covered under each self-separation and the state with continuous counter-rotating shape and yarn axle almost parallel by polyester yarn B, and it can give the bulkiness and the flexibility of the like staple fiber yam of deficiency in aforementioned boundling portion to cloth and silk.
The apparent filament fiber number (average fineness that has thickness inequality person on the length direction) of antistatic polyester composit false twisting processing yarn of the present invention or be not particularly limited as the total fiber number of strand is that the scope of 30~300dtex is suitable but the filament fiber number is 1.5~5.0dtex, total fiber number.
The fiber number of stretch yarn and partially oriented yarn should not selected according to purposes, but usually with regard to total fiber number, can be coiling yarn 〉=heart yarn, and especially preferably making the former is that 30~400dtex, the latter are 20~150dtex.
In addition, the polyester filament yarn X of antistatic polyester composit false twisting processing yarn of the present invention and the yarn of polyester filament yarn Y are grown the scope that differs from 5~20%, more preferably 10~15%, are preferred obtaining in the excellent Texturized sense of Si Bennaizi.
When using the above antistatic polyester composit false twisting processing yarn of the present invention that illustrates to make cloth and silk, can implement the twisting of appropriateness as required, woven or knitting is desirable tissue.The gained cloth and silk presents the woven and irrealizable antistatic property of knit goods in the past, and then can obtain possessing the fluffy sense of spinning sample, the flexible touch and the elasticity on surface, the product with elastic quality, so preferred.
Below the application's the 3rd working of an invention mode is elaborated.
The application the 3rd invention is that antistatic polyester mixes and knits yarn, it is characterized in that, comprise antistatic polyester filament yarn X, with polyester filament yarn Y, and satisfy following (i)~(condition vi),
(i) antistatic polyester filament yarn X is the core-sheath-type polyester complex fiber that core is made of copolyester B polyester A, sheath portion, and polyester A comprises antistatic polyester, in this antistatic polyester, with respect to aromatic polyester 100 weight portions, contain represented poly (oxyalkylene) base system polyethers 0.2~30 weight portion of (a) following general formula (1) and (b) be essentially non-reacted organic ion compound 0.05~10 weight portion as antistatic additive with this polyester.
(ii) the single thread fiber number of polyester filament yarn X is below the 1.5dtex,
(iii) mixing the frictional electrification voltage of knitting yarn is below the 2000V,
(iv) mix knit yarn be successively via air interweave operation, lax heat treatment step and,
(v) the mixed ratio of knitting of polyester filament yarn X and polyester filament yarn Y is 8: 2~6: 4,
(vi) polyester filament yarn X constitutes outer portion, the polyester filament yarn Y formation internal layer portion of knitting yarn of mixing,
R 2O-(CH 2CH 2O)n(R 1O)m-R 2?(1)
[in the formula, R 1Be alkylidene or the substituted alkylene of carbon number more than 2, R 2Be the monovalence alkyl of hydrogen atom, carbon number 1~40, the monovalence hydroxyl hydrocarbon of carbon number 2~40 or the monovalence acyl group of carbon number 2~40, n is the integer more than 1, and m is the integer more than 1].
Constitute polyester of the present invention mix knit yarn, antistatic polyester multifilament textile X is the core-sheath-type polyester complex fiber that core is made of copolyester B polyester A, sheath portion, this polyester A, B are the identical polyester of polyester A, B that uses in the core-sheath-type composite fibre with the application's the 1st invention.
And then the polyester A that requires the core/sheath portion in the cross section of polyester mutifilament yarn X and the area ratio of polyester B are 5: 95~80: 20 scope.The area ratio was less than 5: 95 o'clock, the embodiment of the antistatic property that is got by polyester a is insufficient, greater than 80: 20 o'clock, when then implementing the alkali decrement more than 10%, the antistatic polyester meeting stripping of core, antistatic property reduces, and the intensity of stretch yarn also reduces simultaneously, becomes below the 3.0cN/dtex, undercapacity when being made as cloth and silk, therefore be unsuitable for the purposes of desired strengths such as motion dress material, purposes is restricted, so not preferred.
Making polyester of the present invention mixes when knitting yarn, at first, as polyester filament yarn X ', employing utilizes present known compined spinning apparatus, higher spinning speed about aforementioned polyester a and b divided with 2000~5000m/ carry out spinning and polyester stretch yarn (usually, be called intermediate orientation yarn POY) not, perhaps use low oriented polyester that spinning speed about dividing with 1000m/ carries out spinning not stretch yarn or yarn that the intermediate orientation yarn is stretched and obtains with low range.
On the other hand, as polyester filament yarn Y ', preferably using boiling water shrinkage is polyester filament stretch yarn more than 8.0%, and then preferably to use boiling water shrinkage be 10~16% polyester filament stretch yarn.
As described polyester filament, but preferred illustration do not carry out heat setting the polyester filament stretch yarn, comprised copolymerization as the polyester filament stretch yarn of the polyester about 5~15 moles of % of for example M-phthalic acid of the 3rd composition.
As the fiber number of polyester filament yarn Y, preferred 2~10dtex.Then mixing the intensity of knitting yarn less than 2dtex can reduce, and so then quality hardening when surpassing 10dtex is not preferred.
Fig. 3 is that expression is used to make the front sketch that mixes an example of the device of knitting yarn of the present invention, polyester filament yarn X ' that will spontaneous stretching, draw together with polyester filament yarn Y ' by implementing lax heat treatment, by being arranged on the nozzle 3 that interweaves between donor rollers 1 and the 1st carry-over pinch rolls (warm-up mill) 2, under overfeeding, interweave.
In this device, the 1st carry-over pinch rolls 2 are heated, and between donor rollers 1 and the 1st carry-over pinch rolls 2, above-mentioned 2 kinds polyester filament yarn is by overfeeding, so circumvolution is subjected to lax heat treatment and spontaneous stretching in the polyester filament X ' of the 1st carry-over pinch rolls 2 on this roller.Then,, implement the 2nd lax heat treatment and mix the heat fixation of knitting yarn, batch and be package 6 by being arranged at the noncontact heater 5 between the 1st carry-over pinch rolls 2 and the 2nd carry-over pinch rolls 4.
When above-mentioned 2 kinds polyester filament yarn is interweaved, preferably use the longitude and latitude of 60~70/m staggered, therefore making over feed rate(OFR) usually is 1.0~1.5%, suits.
In addition, as above-mentioned example, with 2 heating of the 1st carry-over pinch rolls, implement lax heat treatment thereon when carrying out spontaneous stretching, it is compact that device becomes, so preferably, but compare with the over feed rate(OFR) that interweaves at nozzle 3 places that are suitable for interweaving, carry out the required over feed rate(OFR) of spontaneous stretching (relaxation rate) by lax heat treatment when bigger, carry-over pinch rolls also can further be set in the downstream of the 1st carry-over pinch rolls 2, and and these carry-over pinch rolls between implement the lax heat treatment of regulation.In addition, with the 1st carry-over pinch rolls 2 during as warm-up mill, it is littler than the diameter that strand advances side to make the strand of this roller 2 go out the diameter of side, and heat-treats with the over feed rate(OFR) (relaxation rate) of regulation on this roller.
The lax heat treated temperature and the over feed rate(OFR) (relaxation rate) of the spontaneous stretching of polyester filament yarn X ' according to which kind of yarn of use are changed as polyester filament yarn X ', for example, the intermediate orientation yarn (POY) that the spinning speed that use divides with 3000~3500m/ has carried out spinning, when relaxing heat treatment on the 1st carry-over pinch rolls (warm-up mill) 2, preferably to make roll surface temperature be 100~130 ℃, make over feed rate(OFR) (relaxation rate) is 1.0~1.5%.
The lax heat treatment that utilizes the 2nd stage of noncontact heater 5 is to be used for of the present invention mix knitted yarn and given the heat fixation of the characteristic of the spinning sample fabric that is suitable for making high resilience simulate wool sense of touch and handle, preferably 220 ℃~240 ℃, handle with 1.5~2.0% over feed rate(OFR), the processing time is generally 0.01~0.30 second.The gained polyester mixes the boiling water shrinkage of knitting yarn and is generally about 5~13%.As noncontact heater 5, can use slit heater, pipe heater etc.
Of the present invention mixing knitted in the yarn, after the polyester filament yarn X ' of the spontaneous stretching by lax heat treatment is interweaved with polyester filament yarn Y ', relax heat treatment so that the spontaneous stretching of polyester filament yarn X ', make polyester filament yarn Y ' carry out thermal contraction simultaneously, thus, can when the 2nd relaxes heat treatment, not contact under the situation of noncontact heater 5 by strand, stably make the mixed yarn of knitting of polyester, reduce the generation of broken end.
Polyester filament yarn X ' is relaxed heat treatment separately with after making it spontaneous stretching and carrying out heat fixation by the lax heat treatment in the 2nd stage, interweave with polyester filament yarn Y ' again and make polyester and mix and to knit in the method for yarn, when utilizing the noncontact heater to carry out the 2nd lax heat treatment, because strand contacts with the noncontact heater, it is also many to break end, so be not suitable for.
For the mixed yarn of knitting of polyester of the present invention, preferred single thread fiber number is that following ultra-fine fiber number of 1.5dtex and the polyester filament yarn X that contains antistatic additive are located opposite from the mixed outside of knitting yarn, polyester filament yarn Y mixes the inboard of knitting yarn with respect to being positioned at, in addition, polyester filament yarn X knits than (weight ratio) with the mixed of polyester filament yarn Y, the viewpoint of expanding from dark color, in weight ratio in 8: 2~5: 5 scope.Be preferably 8~6: 2~4.During for this scope, sense of touch, quality, soft feeling, intensity, etc. obtain balance, have good flexibility, resilience, sense of touch when being made as cloth and silk.
In addition, also preferably will be heat-treated in the temperature more than 100 ℃ by the gained woven and knit goods knit yarn or this fiber manufacturing that mixes of the present invention, be the suitable arrangementization due to the migration of polyethers and contained as required various additives with contained polyoxyethylene in the stabilisation of promotion structure and the fiber.And then also can and use lax heat treatment etc. as required
In addition, as required, can implement to process after the suitable hydrophiling to mix the woven and knit goods of knitting yarn or this fiber manufacturing by antistatic polyester of the present invention, and so be preferred.As processing after this hydrophiling, preferably for example can adopt, the method of handling with the aqueous liquid dispersion of the polyester polyether block copolymer that comprises terephthalic acid (TPA) and/or M-phthalic acid or their lower alkyl esters, low-grade alkylidene glycol and poly alkylene glycol, or hydrophilic monomers such as acrylic acid, methacrylic acid are carried out glycerol polymerization, then with method of its sodium saltization etc.
It is below the 2000V that mixed antistatic behaviour of knitting yarn of the present invention needs frictional electrification voltage.If then the generation of static is big more than the 2000V, when using, dress feels bad, and not preferred on safety yet.
Then, the application's the 4th working of an invention mode is elaborated.
The application's the 4th invention mixes the manufacture method of knitting yarn for antistatic polyester, it is characterized in that, with percentage elongation (ELA) is more than 80%, elastic recovery rate (ERA) during 10% stretching is below 50%, stretching modulus of rigidity (EMA) is below the 5.89GPa, crystallization degree (XpA) is more than 25%, boiling water shrinkage (BWSA) is below 3%, thermal stress under 160 ℃ (TSA) is below the 0.44mN/dtex, and satisfy following (i)~the antistatic polyester filament yarn X ' of important document relax after the heat treatment, be below 40% with percentage elongation (ELB) again, stretching modulus of rigidity (EMB) is more than the 7.85GPa, boiling water shrinkage (BWSB) is more than 5%, thermal stress under 160 ℃ (TSB) is carried out doubling for the above polyester filament yarn Y ' of 0.88mN/dtex, so that the weight ratio of polyester mutifilament yarn X ' and polyester mutifilament yarn Y ' is 45/55~70/30, carry out interleaving treatment then
(i) the core-sheath-type polyester complex fiber that constitutes by copolyester B by polyester A, sheath portion for core of antistatic polyester multifilament textile X ', and polyester A comprises antistatic polyester, in this antistatic polyester, with respect to aromatic polyester 100 weight portions, contain represented poly (oxyalkylene) base system polyethers 0.2~30 weight portion of (a) following general formula (1) and (b) be essentially non-reacted organic ion compound 0.05~10 weight portion as antistatic additive with this polyester
(ii) the single thread fiber number of polyester mutifilament yarn X ' is below the 1.5dtex,
R 2O-(CH 2CH 2O)n(R 1O)m-R 2?(1)
[in the formula, R 1Be alkylidene or the substituted alkylene of carbon number more than 2, R 2Be the monovalence alkyl of hydrogen atom, carbon number 1~40, the monovalence hydroxyl hydrocarbon of carbon number 2~40 or the monovalence acyl group of carbon number 2~40, n is the integer more than 1, and m is the integer more than 1].
Constitute polyester of the present invention mix knit yarn, antistatic polyester multifilament textile X ' is the core-sheath-type polyester complex fiber that core is made of copolyester B polyester A, sheath portion, this polyester A, B are the identical polyester of polyester A, B that uses in the core-sheath-type composite fibre with the application's the 1st invention.
It is more than 80% that above-mentioned antistatic polyester filament yarn X ' needs percentage elongation (ELA), be preferably 100~200%, elastic recovery rate (ERA) when needing 10% to stretch is below 50%, is preferably below 40%, and needing stretching modulus of rigidity (EMA) is 5.89GPa(600kg/mm 2) below, be preferably 1.96~4.91GPa(200~500kg/mm 2), needing crystallization degree (XpA) is more than 25%, is preferably 36~60%, the thermal stress (TSA) under needing 160 ℃ is 0.44mN/dtex(50mg/de) below, and then to need boiling water shrinkage (BWSA) be below 3%.
When showing above-mentioned characteristic, antistatic polyester filament yarn X ' is becoming float state to mixing to knit when yarn carries out heat treated, and applies loading at draw direction and also do not have the stress burden and only help bulkiness to improve, and the result has suppressed the generation of fold.
Antistatic polyester filament yarn X ' with above-mentioned characteristic, can be for example, utilize present known compined spinning apparatus, with aforesaid polyester a and b in 280~300 ℃ of following fusions of temperature, discharge from the spinning nozzle fusion, and give finish to the strand that spins of cooling curing, the use air jet hole is the device that longitude and latitude interlocks of giving more than 3 holes, the air of expulsion pressure 0.1~0.3MPa with give longitude and latitude staggered after, via preheat roll below the glass transition temperature that is set in polyester and draw roll (preheat roll hauling speed: 1500~2500m/ branch, stretching ratio: 1.1~1.5) temporarily batch on winder.
Then, with the gained stretch yarn with speed 500~1400m/ branch, via being heated to 70~110 ℃ preheat roll and being set in 170~240 ℃ contactless heater, implement heat setting (stretching ratio 1 is with the next relaxation heat setting that becomes) and obtain with 0.8~1.1 times stretching ratio.
Then, as constituting the polyester filament yarn Y ' (abbreviating filament yarn Y ' sometimes as) that mixes other composition of knitting yarn of the present invention, the loading of main burden draw direction and keep stability in morphological stability or the back manufacturing procedure, thereby to need percentage elongation (ELB) be below 40%, be preferably below 30%, needing stretching modulus of rigidity (EMB) is 7.85GPa(800kg/mm 2) more than, be preferably 8.83~14.7GPa(900~1500kg/mm 2).In addition, in order to show good bulkiness by heat treatment, needing boiling water shrinkage (BWSB) is more than 5%, be preferably 7~20%, and then, when after being made as cloth and silk, carrying out heat setting with pin stenter etc., not to aforementioned polyester filament yarn X ' stress application, and the reduction of inhibition quality, need make the thermal stress (TSB) under 160 ℃ be 0.88mN/dtex(100mg/dtex) more than, be preferably 1.76mN/dtex(200mg/dtex) more than.
For filament yarn Y ', for example, when the not drawing of fiber that will comprise aforementioned polyester stretches, can suitably regulate its draft temperature or stretching ratio etc. with above-mentioned characteristic.
For example, percentage elongation or modulus of rigidity are regulated by stretching ratio, and the heat-setting condition of boiling water shrinkage when stretching regulated and got final product.When particularly the expectation height shrank, non-plate stretching (non-plate drawing) etc. was suitable.Thermal stress can be by stretching ratio or the heating-up temperature when stretching and not the spinning speed of drawing of fiber regulate.But, when the spinning hauling speed is too high, the thermal stress after the stretching is uprised, so preferably divide following, preferred 1700m/ to divide the following low not drawing of fiber that spins speed to stretch to 2500m/.Should illustrate, the method for copolymerization the 3rd composition in polyester is arranged, for example, during copolymerization M-phthalic acid composition, can easily obtain having the product of high shrinkage character as other method of regulating above-mentioned characteristic.
Knit yarn for of the present invention mixing, after heat treatment that above-mentioned antistatic polyester filament yarn X ' is relaxed, need interweave with mixing with polyester filament yarn Y ' and knit.To strand implement to give thermal deformation, for example false twist crimping processing is not preferred, described method can not obtain the fold recovery effects.Its reason is speculated as, first, heat treated in the false twist crimping processing, stretch, reverse etc. causes the rerum natura of polyester filament yarn X ' to change, thereby percentage elongation reduces, thermal stress uprises or elastic recovery rate improves, thereby the character that forfeiture is extended is with a swish given when curling polyester filament yarn X ', interweave or resistance (opposing) increase with adjacent yarn, in fabric tissue, the position of departing from yarn is difficult to reinstatement, and easily fold takes place during cloth and silks such as formation fabric.
Should illustrate, in utilizing the situation that interweaves of aerojet, the injection direction of air can be and the rectangular direction of yarn, also can spray along the direct of travel of yarn, but can obtain the more excellent product of gloss by the former, then can obtain the soft product of quality by the latter.
Further, between polyester filament yarn X ' and the polyester filament yarn Y ' the overfeeding difference can be set and carry out air combined processing, but difference is when excessive, then coil is a large amount of easily produces, thereby adopts roughly the same over feed rate(OFR) usually.
The compositely proportional of polyester filament yarn X ' and polyester filament yarn Y ' (mix and knit ratio) in the weight ratio of polyester filament yarn X ', polyester filament yarn Y ', need be 45/55~70/30.
Especially, the ratio of polyester filament yarn X ' is many more, then is easy to generate effect of the present invention more, thereby in the part by weight of polyester filament yarn X ', polyester filament yarn Y ', preferred especially 55/45~70/30.Should illustrate that now for polyester filament yarn X ', polyester filament yarn Y ', each is that example is illustrated with 1 rhizoid bar, but from needless to say be the strand that also can use more than 2, in brief, so long as satisfy fiber, then use how many rhizoid bars can as the rerum natura of important document of the present invention.
Further, even the 3rd strand that the discontented unabridged version of interpolation is invented described above-mentioned rerum natura carries out compound also passable.For example, can composition metal plating fiber or carbon particle sneak into fiber, giving electric conductivity, but the ratio of such fiber is when too much, restorative improvement becomes insufficient as the fold of purpose of the present invention, so it is desirable to and be up to 30% with rate.
Should illustrate, the antistatic behaviour core-sheath-type polyester fiber that uses in the application's the 1st invention~the 4 invention, on its filament cross section, the projection coefficient that preferably has 3~8 following formulas definition be 0.3~0.7, from the outstanding laterally fin of fibre section core
The projection coefficient=(a1-b1)/a1
A1: from the length on inscribed circle center to the fin summit of fibre section inner surface
B1: the inscribe radius of a circle of fibre section inner surface (core extrapolation inscribed circle).
Polyester complex fiber of the present invention with above-mentioned characteristic and cross sectional shape, can tolerate draw false twisting and add the impact that is subjected to man-hour, even under common condition, carry out draw false twisting, also can under adding the few condition of generation of the broken end (processing broken yarn) in man-hour and fluffing, draw false twisting stretch, because polyether polyols is that antistatic additive exists with elongated bar form on the fiber axis direction fully, so antistatic behaviour is good.In addition, for gained draw false twisting processing yarn, the flat degree of its fiber cross section appropriateness on the fiber axis direction is disperseed, on the fiber axis direction, become and fibre section inequality, form the big fiber assembly in space between fiber, bring the effect of the washing resistance raising of water-absorbing fast-drying performance and this performance.Further, the flat degree in the fibre section fiber assembly that appropriateness is disperseed on the fiber axis direction also has the performance of bringing the natural dry feeling in the cloth and silk simultaneously.
In addition, water absorbing properties, antistatic behaviour and the process stability of above-mentioned antistatic behaviour core-sheath-type polyester fiber are good.Its reason is still indeterminate, but can be presumed as follows: be used as the core antistatic additive by using hydrophilic polyether polyols system and ionic compound as antistatic additive, cause water imbibition to be promoted to more than single water imbibition by the capillarity due to the projection of given shape, in addition, when spin-drawing, particularly when stretching, resistance decreasing between fiber, so antistatic additive is stretched on the fiber axis direction equably, become and have proper aspect ratio, fluffing simultaneously takes place few, and process stability is good.
The projection coefficient of the filament cross sectional shape of antistatic behaviour core-sheath-type polyester fiber (concrete example is Fig. 5) is 0.3~0.7, more preferably 0.4~0.6.Requirement presents following shape, and promptly the number that exists from the outstanding laterally fin of fibre section core (Fig. 5 1) is 3~8, is preferably 4~6.
This projection coefficient does not have the function that forms sufficient capillary interstice on the fibre section after the draw false twisting processing less than 0.3 fin, can not embody the water-absorbing fast-drying performance.And then this short and small fin diminishes because cloth and silk is applied the anchor effect of suction during finishing agent, so there is the tendency of the washing resistance reduction that makes this finishing agent.In addition, the quality of cloth and silk becomes smooth paper sample.On the other hand, the projection coefficient surpasses 0.7 fin, concentrates machine tensions on man-hour, this fin easily because draw false twisting adds, so produce the partial destruction of fibre section, can not form capillary fully, and it is insufficient that water absorbing properties becomes.In addition, broken end in the draw false twisting operation (processing broken yarn) or fluffing also take place frequently.
Should illustrate, even the projection coefficient is 0.3~0.7 fin,, then is closed in inboard fibre section part and can only forms maximum 1 if when the number of this fin is 1~2 on the filament cross section, so can not embody sufficient capillarity, it is insufficient that water absorbing properties becomes.In addition, the quality of cloth and silk also becomes smooth paper sample.On the other hand, when surpassing 8, the machine tensions that draw false twisting adds on man-hour, the generation fin is concentrated, and causes the partial destruction of fibre section, can not fully form capillary, and it is insufficient that water absorbing properties becomes.In addition, broken end in the draw false twisting operation (processing broken yarn) or fluffing also take place frequently.Should illustrate that the projection coefficient also can exist above 8 less than 0.3 fin.
Above Shuo Ming antistatic behaviour core-sheath-type polyester complex fiber of the present invention, can make by the tap of regulating known core sheath composite spinning machine, for example, can form the radius (a2 of Fig. 6) that portals with circular row, central point to fin that this circular row is portalled and form with the length (b2 of Fig. 6) of the leading section of tap etc. by changing core, be 0.3~0.7 mode and setting arbitrarily with the projection coefficient of fibre section.In addition, by changing the temperature and/or the cooling air quantity of spill spin block (spin block), the also projection coefficient in controlling fiber cross section to a certain extent.
In addition, the antistatic behaviour core-sheath-type polyester fiber that uses in the 1st invention~the 4 invention for the application, requiring the cross section vertical with the single thread length direction is flat pattern, have the shape that 3~6 circular section single thread engage in the vertical, and the bonding part is formed with necking section (constricted part) (with reference to Fig. 7).
In the situation of the shape that common circular section single thread or 2 circular section single thread engage, core-sheath-type polyester flat cross section fiber in the fabric is difficult to be formed on the set form of expanding on the cross direction, the space (tissue space) that is formed by warp thread and weft yarn becomes big, its result, light passes through from this space, might can not get anti-fully observability, so not preferred.On the contrary, when surpassing 7, then throwing becomes difficult, so not preferred.
Then, aforesaid necking section shown in pattern ground among Fig. 8, is meant the part that the length of minor face shortens.In the described necking section,,, be preferably the degree of depth of (preferred more than 1.1) more than 1.05 in the ratio B/C of maximum (B) with the minimum of a value (C) of the length of minor face as concave depth.In addition, among Fig. 8, illustration recess be formed at the example of both sides, but also can only on a side sidepiece, form recess.And the number of this necking section need be for more than 2, and the necking section is 1 and can not get gratifying anti-observability can not get the diffuse reflection of sufficient light or the refraction of transmitted light in the next necking section, so not preferred.As long as the number of this necking section is then to be not particularly limited more than 2, but when considering throwing, 3~5 is suitable.Should illustrate that Fig. 8 is illustrative to be that the necking section is 2 a situation.
For above-mentioned antistatic behaviour core-sheath-type polyester fiber, because its shape of cross section is special flat, so when weaving, owing to the contact pressure of fabric tissue point, and the structure that has densification and on cross direction, expand.Its result, the space that is formed by warp thread and weft yarn diminishes, and reduces from the throughput of the light in this space.At this moment, the transmitted light generation diffraction of the trace by this space by interfering mutually with adjacent transmitted light, and obtains excellent anti-visual effect.
Further, because making the shape of cross section of long filament is the flattened with specific necking section, and the content that makes delustering agent is below the specified quantitative, so compare with smooth flat cross section yarn, circular section yarn, triangle section yarn with fiber number, the diffuse reflection of light or the refraction that sees through the transmitted light of long filament become big, can obtain excellent anti-visual effect and do not damage daylighting.
In addition, core-sheath-type polyester flat cross section fiber is owing to having the structure of expanding, so the flexural rigidity step-down also has been endowed soft quality on cross direction.And then on fabric tissue point, necking section (recess) is difficult to contact other yarn, so the less traction of warp thread and weft yarn can obtain further tender texture than having smooth flat pattern person.
Embodiment
Below, enumerate embodiment and comparative example and further specify the present invention, but scope of the present invention, only otherwise exceed its purport, be not subjected to their any qualification.Should illustrate that each characteristic value among the embodiment is measured with following method.
(in I. the application the 1st invention, copolyester B has been copolymerization the embodiment of polyester of organic system ultraviolet radiation absorption composition)
(1) inherent viscosity
Be dissolved in o-chlorphenol, use Ubbelohde viscometer to measure at 35 ℃.
(2) spinning broken yarn
Carry out 1 all melt spinnings with composite spinning equipment, the number of times of broken yarn carried out record, with the spinning broken yarn number of times of per 1 hammer on the 1st as the spinning broken yarn.Wherein, the broken yarn due to artificial or the mechanical reason is got rid of from the broken yarn number of times.
(3) draw false twisting broken yarn
Building HTS-15V(with Supreme Being people's making mechanism 216 hammers is 2 heater false twist processing machines, contactless heater specification), implement 1 all draw false twisting processing continuously, with 1 of draw texturing machine, per 1 day broken yarn number of times is as the draw false twisting broken yarn.Wherein, yarn is linked before and after due to broken yarn (knotting broken yarn) or the broken yarn due to the broken yarn when automaticallying switch etc., artificial or mechanical reason from the broken yarn number of times, get rid of.
(4) stretching broken yarn
Implement continuously 1 all stretch process, with 1 of stretching-machine, per 1 day broken yarn number of times as the draw false twisting broken yarn.Wherein, yarn is linked before and after due to broken yarn (knotting broken yarn) or the broken yarn due to the broken yarn when automaticallying switch etc., artificial or mechanical reason from the broken yarn number of times, get rid of.
(5) birefringence
According to well-established law, use light microscope and compensator, by obtaining in the optical path difference of the observed polarisation of fiber surface.
(6) intensity of strand, percentage elongation
Measure according to JIS L-1013-75.
(7) crimp percent
Polyester false-twisted yarn sample is applied the tension force of 0.044cN/dtex, and batch, make the hank knotting of about 3300dtex in the hank knotting frame.In 2 loadings of an end load 0.0177cN/dtex and the 0.177cN/dtex of this hank knotting, measure) through the length S0(cm after 1 minute.Then, under the state of the loading of removing 0.177cN/dtex, in 100 ℃ boiling water, handled 20 minutes.Remove the loading of 0.0177cN/dtex after the boiling water treating, air dry is 24 hours under free state, and the loading of load once more 0.0177cN/dtex and 0.177cN/dtex is measured through the length after 1 minute, as S1(cm).
Then, remove the loading of 0.177cN/dtex, measure,, calculate crimp percent, be expressed as the mean value of 10 measured values with following formula as S2 through the length after 1 minute.
Crimp percent (%)=[(S1-S2)/S0] * 100
(8) fluffing number
Use the Toray(strain) system DT-104 type fluffing counting device, with drawn polyester yarn sample METHOD FOR CONTINUOUS DETERMINATION 20 minutes under the speed of 500m/min, instrumentation takes place plays approximate number, is expressed as the number of long per 1 myriametre of sample.
(9) quality
(soft feeling)
1 grade: have soft and soft sense of touch
2 grades: lack soft feeling a little but can feel resilience
3 grades: coarse sense of touch or the sense of touch of hardening.
(10) charging property test method
A method (half-life determination method)
After the strand of gained carried out drum type brake knitting (tube Knitting body), dyeing, damping, test film after corona discharge field is charged, is measured this electrified voltage by charge decay analyzer (static honest meter) and decayed to for 1/2 time of ending (second).Time (second), short more then antistatic property was judged as excellent more.
B method (frictional electrification voltage determination method)
While making the test film rotation use friction cloth to rub, measure the electrified voltage that produces.
Carry out according to L1094 charging property test method B method (frictional electrification voltage determination method).
For antistatic effect, as long as frictional electrification voltage is then realized antistatic effect for about 2000V following (preferred 1500V is following).
(11) brightness index
As brightness index L, utilize L*a*b* to represent to be the method for expressing of the object color of representing to be with L*u*v* with JIS-Z-8729() shown in L*a*b* represent to be to represent.
(12) ultraviolet transmittance
Measure transmissivity with the system spectrophotometer MPC-3100 of Shimadzu Seisakusho Ltd., measure the UV-preventing rate of wavelength 380nm.
(13) heat insulating ability
Under the constant-temperature constant-humidity environment of 20 ℃ of temperature, humidity 60%RH, use 200W reflectoscope light source as energy source, 50cm shines from height, uses the temperature at the back side of the cloth and silk of thermocouple measurement after 180 seconds.This temperature is then for good more than 30 ℃.
(manufacturing of polyester A)
Add in the ester exchange reaction jar with 100 parts of terephthalic acid (TPA) dimethyl esters, 60 parts of ethylene glycol, calcium acetate 1 water salt 0.06 part (is 0.066 mole of % with respect to the terephthalic acid (TPA) dimethyl esters) with as the cobalt acetate 4 water salt 0.013 part (is 0.01 mole of % with respect to the terephthalic acid (TPA) dimethyl esters) of toner, this reactant was warming up to 220 ℃ through 4 hours from 140 ℃ under nitrogen atmosphere, the methyl alcohol distillation that generates in the retort is removed to system, carry out ester exchange reaction simultaneously.After ester exchange reaction finishes, add as the tricresyl phosphate methyl ester of stabilizing agent 0.058 part (is 0.080 mole of % with respect to the terephthalic acid (TPA) dimethyl esters) with as 0.024 part of the dimethyl polysiloxane of defoamer to reactant mixture.Then, after 10 minutes, add 0.041 part of antimony trioxide (is 0.027 mole of % with respect to the terephthalic acid (TPA) dimethyl esters) to reactant mixture,, afterwards reactant mixture is transferred in the polymerisation jar on one side one side gold-plating goes excessive ethylene glycol to be warming up to 240 ℃ simultaneously.Then be decompressed to 1mmHg from 760mmHg, be warming up to 280 ℃ from 240 ℃ simultaneously, obtain polyester to carry out polycondensation reaction through 1 hour 40 minutes.
Use above-mentioned polyester, as antistatic additive, under vacuum, add as 4 parts of the polyethylene glycol of the molecular weight 20000 of (a) poly (oxyalkylene) base system polyethers and (b) 2 parts of neopelexes, further carry out polycondensation reaction in 240 minutes, then under vacuum, add 0.4 part of system IRGANOX 1010 of チ バ カ イ ギ ー society, further carry out polycondensation reaction in 30 minutes afterwards as antioxidant.In the polymerisation operation, add antistatic additive, the inherent viscosity of resulting polymers is 0.657, and softening point is 258 ℃.
(manufacturing of polyester B)
The polyester that has used following drying is as polyester B, the polyester of described drying contain comprise with the method for putting down in writing in the Japanese kokai publication sho 62-11744 communique synthetic 2,2 '-TOPOT 2,2 (3, the 1-benzo
Figure 78643DEST_PATH_IMAGE002
Piperazine-4-ketone) organic system ultra-violet absorber 1.0 weight %, not containing titanium dioxide etc. inorganic is ultra-violet absorber and/or reflective agent, and inherent viscosity is 0.65.
(throwing method)
The polyester A and the polyester B of drying are used the well-established law fusion respectively, be supplied to 2 composition composite spinning heads via gear pump.Core and sheath polymer ratio are set at the value of table 1 record.The molten polymer of core of Gong Geiing and sheath portion simultaneously, spinning nozzle from the circular composite spinning hole that is equipped with 72 nozzle bore 0.25mm, use cooling air to carry out cooling curing from common cross-current ejector half spinning tube, while giving the spinning oil boundling is a strand, and draw with the speed of 3000m/min, obtain the polyester stretch yarn not of the 140dtex/72 long filament of birefringence 0.035.
[example I-1]
The polyester that will be obtained by preceding method is stretch yarn not, uses known stretching-machine, with draw speed 600m/ branch, after being stretched to 1.8 times with 80 ℃ of preheat roll temperature, carry out heat setting for 190 ℃ with the slit heter temperature, use the gained stretch yarn to make drum type brake knit goods, measure antistatic behaviour.
Spinning broken yarn during melt spinning is that 3 times/day, stretching broken yarn are 2 times/day.
In addition, the single thread fiber number of the stretch yarn of gained is 1.16dtex, and intensity is 4.8cN/dtex, and percentage elongation is 24%, and the electrified voltage in the charging property of the drum type brake knit goods test B method is 900V, and ultraviolet transmittance is 10%, the L value is 84%.
[example I-2]
The polyester that will be obtained by preceding method is stretch yarn not, use known false twist processing machine, count with false twisting under the condition of 2400T/m, 210 ℃ of heter temperatures, the fast i.e. speed 250m/min of the 2nd outlet roller 11 of yarn, be stretched to 1.8 times of stretching ratios, use the gained false-twisted yarn to make drum type brake knit goods, measure antistatic behaviour.Process stability during melt spinning and antistatic property the results are shown in Table I-1.
Then, use liquid-flow dyeing machine to carry out 20 minutes relaxation processes in this fabric, carry out preboarding then and handle, dye further then, formalize eventually and handle, be made as cloth and silk with boiled water.
The antistatic property of gained cloth and silk is 15 seconds, and when the enforcement official can estimate, the result had the degree of depth very much, and had feeling of high class, for presenting the quality of soft feeling.
[example I-3~I-6, Comparative Example I-1~I-7]
Except implementing, use the method identical to carry out with example I-1 with the condition shown in the Table I-1.
The present invention, particularly very practical to heat resistance in the operation of back, that significantly manifest via high pressure dyeing.And then, as purposes, be suitable for motion purposes, uniform.In addition, because the part of performance antistatic behaviour is besieged, so antistatic composition is being wrapped, distortion reduces, make fluffing not occur, this is considered to keep antistatic behaviour, and the fluffing minimizing in the stretching, productivity ratio improve and the reason that has excellent washing resistance when being made as fabric.
[Table I-1]
Figure 106642DEST_PATH_IMAGE004
(in II. the application the 1st invention, copolyester B has been copolymerization the embodiment of polyester of phosphorus flame retardant composition)
(14) diethylene glycol (DEG) content:
Use hydrazine hydrate (hydrazine hydrate) decomposing polyester composition tablet, use gas-chromatography (ヒ ュ ー レ ッ ト パ ッ カ ー De society's system (HP6850 type)) measure the content of the diethylene glycol (DEG) in this decomposition product.
(15) phosphorus atoms content
Use the system fluorescent X-ray spectrometer ZSX100e of リ ガ Network society type, utilize the fluorescent X-ray method to carry out quantitatively.
(16) anti-flammability
Measure LOI values (limited oxygen index) according to JIS K 7201, being qualified more than 27.
(17) cation stain
It is knitting that the gained filament yarn is carried out drum type brake, 60 ℃ carry out 20 minutes refining after, under the following conditions, carry out dyeing and air-dry in 60 minutes at 130 ℃.Then use small-sized pin stenter 150 ℃ carry out 1 minute heat setting after, make 8 overlapping sample strip, measure the tone L value of this sample strip with マ Network ベ ス society system color colour difference meter, as chromatic index.The L value low more then more display fibers be colored and be heavy colour, being qualified below 40.
Dyestuff AIZEN COLOR CATION BLUE 0.2%owf
Dye leveller acetate 0.3g/L
Sodium sulphate 3.0g/L
[example II-1]
(manufacturing of polyester A)
Implement in the same manner with the manufacture method of polyester B among the embodiment of polyester of organic system ultraviolet radiation absorption composition that has been copolymerization of copolyester B in the application the 1st invention, make polyester B.
(manufacturing of polyester B)
In the mixture of terephthalic acid (TPA) dimethyl esters 100 parts by mass and ethylene glycol 50 parts by mass, add organic phosphorus compound 3.0 parts by mass shown in the following formula (2) as fire retardant, finish ester exchange reaction.
[changing 3]
Figure 475175DEST_PATH_IMAGE005
[R 1Be 2-hydroxyethyl, R 2Be methyl, R 3Be hydrogen]
Then, add antimonous oxide 0.018 parts by mass to reaction product, be transferred to possess agitating device, in the reaction vessel of nitrogen introducing port, pressure-reduction outlet and distilling apparatus, be warming up to 280 ℃, under the high vacuum below the 30Pa, carry out polycondensation reaction, obtain inherent viscosity 0.58dL/g, diethylene glycol (DEG) content is the polyester of 2.46 quality %.The content of phosphorus is 4700ppm.
(throwing)
With the above-mentioned sheath polyester B of portion and dry each personal well-established law fusion of core polyester A, be supplied to 2 composition composite spinning heads via gear pump.Core and sheath polymer ratio are set at the value of table 1 record.The molten polymer of core of Gong Geiing and sheath portion simultaneously, spinning nozzle from the circular composite spinning hole that is equipped with 72 nozzle bore 0.25mm, use cooling air to carry out cooling curing from common cross-current ejector half spinning tube, while giving the spinning oil boundling is a strand, speed with 3000m/min is drawn, and obtains the polyester stretch yarn not of the 140dtex/72 long filament of birefringence 0.035.Be stretched to 1.8 times with known drawing process, obtain yarn of the present invention (single thread fiber number 1.1dtex).
Use the gained yarn to make drum type brake knit goods, measure antistatic behaviour.Then, carry out 20 minutes relaxation processes, after then carrying out preboarding and handling, dye, setting is handled eventually, is made as the cloth and silk that comprises the compound stretch yarn of polyester with boiled water.
The frictional electrification voltage of gained cloth and silk is 900V, and anti-flammability is 28, and when the enforcement official can estimate, the result had the distinctiveness or the degree of depth very much, and had feeling of high class, for presenting the quality of soft feeling.
[Comparative Example I I-1]
Except not using fire retardant, carry out in the same manner with example II-1.
The frictional electrification voltage of gained cloth and silk is 900V, and when the enforcement official can estimate, it was for having the degree of depth very much as a result, and has feeling of high class, presents the cloth and silk of the quality of soft feeling.But anti-flammability is 21.
[Comparative Example I I-2]
Except not using antistatic additive, carry out in the same manner with example II-1.
When the sense of implementing the gained cloth and silk was estimated, it was for unusual distinctiveness and have the degree of depth and have feeling of high class, present the cloth and silk of the quality of soft feeling as a result.Anti-flammability is 28, is good.Yet frictional electrification voltage is 5000V, produces Pi crack static when dress is used.
[Comparative Example I I-3]
Except not using metal organic sulfonate, carry out in the same manner with example II-1.
The frictional electrification voltage of gained cloth and silk is 900V, and anti-flammability is 28, is good, but the enforcement official be can estimate the time, and it is the distinctiveness that do not dye, the cloth and silk of appearance poor as a result.
(in III. the application the 1st invention, the cross sectional shape of antistatic behaviour core-sheath-type polyester fiber is the embodiment of abnormity)
(18) light transmission
After utilizing JISL10556.1A method (illumination 100,000 lx) to measure shading rate (%), obtain light transmission (%) by following formula.Being qualified more than 20%.
(light transmission)=100-(shading rate)
(19) anti-observability
Assay method as daytime, under the environment of indoor 80W fluorescent lamp 700lx, place visible in position apart from anti-observability fabric 20cm, place the estimator at outdoor (sunshine 100,000 lx on daytime) that clip this fabric apart from the position of this fabric 30cm, whether the visual judgement of estimator can confirm aforementioned visible.Determinating reference is as follows: the mood that can judge visible is that ◎, interpretable slightly situation are zero, the situation that can see the profile of visible is △, the situation that can not judge visible for *.
In addition, assay method as night, under the environment of indoor 80W fluorescent lamp 700lx, place visible in position apart from anti-observability fabric 20cm, place the estimator at outdoor (0.2lx at night) that clip this fabric apart from the position of this fabric 30cm, whether the visual judgement of estimator can confirm aforementioned visible.The assay method on determinating reference and daytime is identical.
(20) necking section ratio and flattening coefficient (with reference to Fig. 8)
Necking section ratio:, take the microphotograph in each cross section with single thread every 10m on the fiber axis direction of flat cross section yarn of the present invention 10 places of taking a sample.For whole fibre sections of taking, measure minor axis maximum length B, with the ratio (B/C) of the minimum length C of the minor axis of necking section, represent with the mean value of whole measured values.
Flattening coefficient:, take the microphotograph in each cross section with single thread every 10m on the fiber axis direction of flat cross section yarn of the present invention 10 places of taking a sample.For whole fibre sections of taking, measure major axis promptly the length at the longest position (A), with ratio A/B perpendicular to the maximum length (B) of the minor axis C of major axis, represent with the mean value of whole measured values.
[EXAMPLE III-1]
(manufacturing of polyester A)
Implement in the same manner with the manufacture method of polyester A among the embodiment of polyester of organic system ultraviolet radiation absorption composition that has been copolymerization of copolyester B in the application the 1st invention, make polyester A.
(manufacturing of polyester B)
Implement in the same manner with the manufacture method of polyester B among the embodiment of polyester of organic system ultraviolet radiation absorption composition that has been copolymerization of copolyester B in the application the 1st invention, make polyester B.
(throwingization)
Throwingization is as described below carries out.With dry polymer each personal well-established law fusion in spinning equipment, be supplied to 2 composition composite spinning heads via gear pump.Core and sheath polymer ratio are set at 30/70.The molten polymer of core of Gong Geiing and sheath portion simultaneously, by boring a hole in the nozzle at 4 points (four-crested) flat cross section (3 places, necking section), under 300 ℃ of spinning temperatures, spin, use cooling air to carry out cooling curing from common cross-current ejector half spinning tube, while giving the spinning oil boundling is a strand, draw with 4000m/min, temporarily do not batch and pull on and extend 1.3 times, the shape of cross section that obtains long filament is the flat cross section (B/C=1.2 with 3 necking sections, cross section flatness 3.2) core-sheath-type polyester flat cross section fiber 84dtex/36fil.
The intensity of gained fiber is that 4.5cN/dtex, frictional electrification voltage (B method) are 900V.The shape of cross section of gained single thread is shown in Fig. 7 (e).
Then, this core-sheath-type polyester flat cross section fiber with non-twist, is used longitude and latitude 100%, utilize the weaving method of well-established law, be made as the plain cloth (plain woven fabric) of cover factor 1000, obtain anti-observability fabric of the present invention by the dyeing processing of implementing well-established law.
The light transmission that should prevent the observability cloth and silk is 35%, prevents that observability (daytime) is zero for ◎, anti-observability (night).
[EXAMPLE III-2]
In the EXAMPLE III-1,, carry out in the same manner,, obtain anti-observability fabric by carrying out woven dyeing processing with embodiment 1 except the cover factor that will prevent the observability fabric is changed into 880.
In should anti-observability cloth and silk, the pollen expulsion rate be 97%, light transmission is 40%, anti-observability (daytime) is zero, anti-observability (night) is zero.
[EXAMPLE III-3]
In the EXAMPLE III-1,, carry out in the same manner,, obtain anti-observability fabric by carrying out woven dyeing processing with embodiment 1 except the cover factor that will prevent the observability fabric is changed into 1800.In should anti-observability cloth and silk, the pollen expulsion rate be 98%, light transmission is 25%, anti-observability (daytime) is ◎ for ◎, anti-observability (night).
[EXAMPLE III-4]
In the EXAMPLE III-1, except use implemented 200T/m twisting as the multifilament (A), carry out in the same manner with embodiment 1, by carrying out woven dyeing processing, obtain anti-observability fabric.In should anti-observability cloth and silk, the pollen expulsion rate be 98%, light transmission is 33%, anti-observability (daytime) is zero, anti-observability (night) is zero.
[EXAMPLE III-5]
In the EXAMPLE III-1, except the necking section is 5, similarly carry out.The shape of cross section of gained single thread is shown in Fig. 7 (g).In should anti-observability cloth and silk, the pollen expulsion rate be 99%, light transmission is 34%, anti-observability (daytime) is zero for ◎, anti-observability (night).
[Comparative Example I II-1]
In the EXAMPLE III-1, except the smooth flat cross section (flattening coefficient A/B=3.2) of the shape of cross section of long filament being changed into no necking section, carry out in the same manner, obtain anti-observability fabric with embodiment 1.Fibre strength is that 5.0cN/dtex, frictional electrification voltage are 900V.In should anti-observability cloth and silk, the pollen expulsion rate be 98%, light transmission is 30%, anti-observability (daytime) is △ for △, anti-observability (night).
[Comparative Example I II-2]
In the EXAMPLE III-1, except the shape of cross section of long filament being changed into Fig. 7 (h), carry out in the same manner, obtain anti-observability fabric with embodiment 1.The generation of fluffing in the silk producing procedures is many, produces rate variance, so fail to form fabric.
[Comparative Example I II-3]
In the EXAMPLE III-1, except the shape of cross section of long filament being changed into the circular section of Fig. 7 (b), carry out in the same manner, obtain anti-observability fabric with embodiment 1.Fibre strength is that 6.0cN/dtex, frictional electrification voltage are 900V.In should anti-observability cloth and silk, the pollen expulsion rate be 98%, light transmission is 30%, but anti-observability (daytime) be *, anti-observability (night) is *.
[Comparative Example I II-4]
In the EXAMPLE III-1,, carry out in the same manner, obtain anti-observability fabric except not to polyester A adds antistatic additive.Fibre strength is that 5.0cN/dtex, frictional electrification voltage are 900V.In should anti-observability cloth and silk, the pollen expulsion rate be 15%, light transmission is 35%, anti-observability (daytime) is zero for ◎, anti-observability (night).
[Comparative Example I II-5]
In the EXAMPLE III-1, in making polyester A, contain titanium oxide (Sakai chemical industry, the KA-30) 1.0wt%, carry out in the same manner, obtain anti-observability fabric.Fibre strength is that 4.0cN/dtex, frictional electrification voltage are 900V.In should anti-observability cloth and silk, the pollen expulsion rate be 98%, light transmission is 10%, anti-observability (daytime) is △ for △, anti-observability (night).
[Comparative Example I II-6]
In the EXAMPLE III-1,, carry out in the same manner,, obtain anti-observability fabric by carrying out woven dyeing processing with embodiment 1 except the cover factor that will prevent the observability fabric is changed into 2500.In should anti-observability cloth and silk, the pollen expulsion rate be 98%, light transmission is 15%, anti-observability (daytime) is zero, anti-observability (night) is zero.
[Comparative Example I II-7]
In the EXAMPLE III-1,, carry out in the same manner,, obtain anti-observability fabric by carrying out woven dyeing processing with embodiment 1 except the cover factor that will prevent the observability fabric is changed into 600.In should anti-observability cloth and silk, the pollen expulsion rate be 98%, light transmission is 15%, anti-observability (daytime) for *, anti-observability (night) for *.
(in IV. the application the 1st invention, the cross sectional shape of antistatic behaviour core-sheath-type polyester fiber is for abnormity and implemented the embodiment that false twisting is processed)
(21) boiling water shrinkage
The dipping device of frame girth 1.125m is made the several 20 times hank knotting of volume, applies the overweight of 0.022cN/dtex, hangs in scale plate, measures the initial long L0 of hank knotting.Then, this hank knotting handled 30 minutes in 65 ℃ tepidarium after, put cold hanging once more in scale plate, measure the length L after shrinking, and calculate boiling water shrinkage with following formula.
Boiling water shrinkage=(L0-L)/L0 * 100(%)
(22) projection coefficient
Take the cross section microphotograph of polyester complex fiber, mensuration is calculated the projection coefficient from the length (a1) on inscribed circle center to the fin summit of filament cross section inner surface and the inscribe radius of a circle (b1) of fibre section inner surface with following formula.
The projection coefficient=(a1-b1)/a1
(23) water-absorbing fast-drying (wicking value)
Index as the water-absorbing fast-drying performance, water absorption testing according to JIS L1907 fiber product, 5.1.1 an absorption speed (dripping method) has adopted test cloth surface the second number (wicking value) up to surface reflection do not take place till of water droplet from comprising the polyester false-twisted yarn that drop.Should illustrate that L10 represents to carry out the wicking value (second) after the washing 10 times according to JIS L0844-A-2 method.
(24) processing broken yarn rate
With the system SDS-8 of ス グ ラ ッ グ society type draw false twisting processing machine, to the processing of 10kg volume polyester complex fiber package carrying out draw false twisting, to make the package of 2 5kg volume polyester false-twisted yarns, during with this method running, record broken yarn number of times is with following formula calculating processing broken yarn rate
Processing broken yarn rate=broken yarn number of times/(sowing Move hammer number * 2) * 100.
[EXAMPLE IV-1~IV-3, Comparative Example I V-1~IV-2]
(manufacturing of polyester A)
Implement in the same manner with the manufacture method of polyester A among the embodiment of polyester of organic system ultraviolet radiation absorption composition that has been copolymerization of copolyester B in the application the 1st invention, make polyester A.
(manufacturing of polyester B)
Implement in the same manner with the manufacture method of polyester B among the embodiment of polyester of organic system ultraviolet radiation absorption composition that has been copolymerization of copolyester B in the application the 1st invention, make polyester B.
(throwingization)
Throwingization is as described below carries out.With dry polymer each personal well-established law fusion in spinning equipment, be supplied to 2 composition composite spinning heads via gear pump.Core and sheath polymer ratio are set at the value of Table IV-1 record.
The molten polymer of core of Gong Geiing and sheath portion simultaneously, carry out spinning from the spinning nozzle that has worn 24 groups of tap groups, in the described tap group, slit is wide for 0.10mm and have 4 length (b2 of Fig. 5) from this tap central point to leading section and use tap for the fin of 0.88mm forms, and the radius (a2 of Fig. 5) that core formation is portalled with circular row is 0.15mm.Using the cooling air from common cross-current ejector half spinning tube to carry out cooling curing, is a strand while give the spinning oil boundling, draws with the speed of 3000m/min, and the polyester that obtains the 140dtex/24 long filament is stretch yarn not.
This polyethylene terephthalate composite fibre is arranged on SDS-8 type draw texturing machine (3 frictional disk false-twisting devices of ス Network ラ ッ グ society system, 216 hammers), implement draw false twisting processing with stretching ratio 1.65,175 ℃ of heter temperatures, 3300 times/m of twisting count, draw false twisting speed 600m/min, obtain the polyethylene terephthalate draw false twisting processing yarn of fiber number 84dtex.
The result of charging property test wicking value (L0 and L10), processing broken yarn rate and processing fluffing among EXAMPLE IV-1~IV-3, the Comparative Example I V-1~IV-2 sums up and is shown in the Table IV-1.
[Comparative Example I V-3]
As polyester A, use the polyester B that does not add antistatic additive, carry out in the same manner with EXAMPLE IV-1.
[Comparative Example I V-4]
With spinning nozzle in the EXAMPLE IV-1 is the portal spinning nozzle (circular section nozzle) of group of the circular row that worn 24 groups of common 0.3mm, use cooling air to carry out cooling curing from common cross-current ejector half spinning tube, while giving the spinning oil boundling is a strand, speed with 3000m/min is drawn, and the polyester that obtains the 140dtex/24 long filament is stretch yarn not.
Draw false twisting processing afterwards etc. is undertaken by the method identical with EXAMPLE IV-1.
[Comparative Example I V-5]
Only use the polyester B that does not add antistatic additive, from the circular row that has worn 24 groups of common 0.3mm portal the group spinning nozzle (circular section nozzle), use cooling air to carry out cooling curing from common cross-current ejector half spinning tube, while giving the spinning oil boundling is a strand, speed with 3000m/min is drawn, and the polyester that obtains the 140dtex/24 long filament is stretch yarn not.
Draw false twisting processing afterwards etc. is undertaken by the method identical with EXAMPLE IV-1.
[Table IV-1]
Figure 664848DEST_PATH_IMAGE006
(V. the application the 2nd inventive embodiment)
(27) bulkiness evaluation:
The evaluation of bulkiness is based on following assay method.Promptly, compound spot yarn (composite mottled yarn) is made hank knotting 120 times with dipping device (girth 1.125m) rotation, hang on 3 times loading of this hank knotting weight at an end of the sample that it is converted into 2 foldings, and, cool off then xeothermic 195 ℃ of following heat treatments 5 minutes.Then this strand is filled in the box (radius of curvature of height 2.5cm, width 1.0cm, length 10cm, bottom surface 0.5cm), makes it loading upper cover (3 times of weight of hank knotting), the volume (Vcm in the time of thus 3) with the weight (Wg) of hank knotting (mix knit sliver), calculate by following formula.
Bulkiness (cm 3/ g)=V/W
This value be 50 when above with bulkiness as " very ", less than 50 o'clock as " bad ".
(28) texture score: flexibility, dry feeling, the Texturized outward appearance of Si Bennaizi comprehensive
Each assessment item for quality, in the sense of utilizing 5 skilled people to pass judgment on is estimated, all be judged to be very good conduct (zero), be judged as good conduct (△) more than 3 people, be judged to be bad conduct (*) more than 3 people, mark in three stages.
(28) yarn is long poor: calculate by following formula,
Long poor (%)=(L of yarn S-L C)/L C* 100
(wherein, L SAnd L CExpression will mix knits polyester yarn A contained among the 5cm that yarn is cut at an arbitrary position and the mean value of polyester yarn B whole filament yarn lengths separately).
[EXAMPLE V-1]
(manufacturing of polyester A)
Implement in the same manner with the manufacture method of polyester A among the embodiment of polyester of organic system ultraviolet radiation absorption composition that has been copolymerization of copolyester B in the application the 1st invention, make polyester A.
(manufacturing of polyester B)
Implement in the same manner with the manufacture method of polyester B among the embodiment of polyester of organic system ultraviolet radiation absorption composition that has been copolymerization of copolyester B in the application the 1st invention, make polyester B.
(throwing of polyester filament yarn X)
Throwingization is as described below carries out.With dry polymer each personal well-established law fusion in spinning equipment, be supplied to 2 composition composite spinning heads via gear pump.The core composition of above-mentioned making and sheath composition polymer ratio are set at the value of table 1 record.The molten polymer of core composition of Gong Geiing and sheath composition simultaneously, spinning nozzle from the circular composite spinning hole that worn 36 nozzle bore 0.25mm, use cooling air to carry out cooling curing from common cross-current ejector half spinning tube, while giving the spinning oil boundling is a strand, speed with 3000m/min is drawn, and obtains the not stretched polyester multifilament of 120dtex/36 long filament.Gained yarn characteristic is as described in Table 1.
(throwing of polyester filament yarn Y)
On the other hand, be that 0.64 polyethylene terephthalate is discharged from the spinning nozzle fusion with inherent viscosity, give finish after making this discharge strand cooling curing, draw, obtain the partially oriented not stretched polyester filament yarn of 150dtex/48 long filament with 1000m/ minute speed.
With gained stretched polyester filament yarn and partially oriented polyester filament yarn disentanglement and draw together separately not, carry out interleaving treatment and draw false twisting processing with the operation of Fig. 1.
Promptly, aforementioned 2 strands are supplied to feed roller 6, and the 1st outlet roller 8 between, carry out interleaving treatment with over feed rate(OFR) 3.0%, pressure pneumatics power 0.25Mpa by the nozzle 7 that interweaves, give interweaving of 60/m, be supplied to false twist zone via roller 8 then, batch in winder, obtain the false-twisted yarn bar of 190dtex/84 long filament with the condition that 1.5 times of stretching ratios, 450 ℃ of heter temperatures, yarn speed 550m/ divide.
With the microscopic examination of gained false-twisted yarn, it is the false-twisted yarn based on structure shown in Figure 2 [by the structure of the order of mutual twist yarn shape coiling portion (I)-portion that interweaves (II)-Kai fibre portion (III) formation] as a result.
The gained strand is used for warp thread and weft yarn, and woven is Habutae, implements refining, heat setting, dyeing according to well-established law, obtains not figuratum DYED FABRICS.Evaluation result is shown in table 1.
[comparative example V-1~V-5]
Change into shown in the table 1 condition except the amount of the antistatic additive that will use, implement in the same manner with EXAMPLE V-1.Evaluation result is shown in Table V-1.
[Table V-1]
(VI. the application the 3rd inventive embodiment)
(29) quality of cloth and silk
To mix knit the plain cloth and dyeing that yarn is made into 60/cm of warp thread, 35/cm of weft yarn after, estimate quality.
(soft feeling)
1 grade: have soft and soft sense of touch
2 grades: lack soft feeling a little but can feel resilience
3 grades: coarse sense of touch or the sense of touch of hardening.
[example VI-1]
(manufacturing of polyester A)
Implement in the same manner with the manufacture method of polyester A among the embodiment of polyester of organic system ultraviolet radiation absorption composition that has been copolymerization of copolyester B in the application the 1st invention, make polyester A.
(manufacturing of polyester B)
Implement in the same manner with the manufacture method of polyester B among the embodiment of polyester of organic system ultraviolet radiation absorption composition that has been copolymerization of copolyester B in the application the 1st invention, make polyester B.
(throwingization)
Throwingization is as described below carries out.With dry polymer each personal well-established law fusion in spinning equipment, be supplied to 2 composition composite spinning heads via gear pump.Core and sheath polymer ratio are set at core/sheath portion=30/70.The molten polymer of core of Gong Geiing and sheath portion simultaneously, spinning nozzle from the circular composite spinning hole that is equipped with 72 nozzle bore 0.25mm, use cooling air to carry out cooling curing from common cross-current ejector half spinning tube, while giving the spinning oil boundling is a strand, speed with 3000m/min is drawn, and obtains 90dtex/72 long filament (filament fiber number: polyester intermediate orientation yarn (POY) (polyester mutifilament yarn X ') 1.25dtex).
On the other hand, with inherent viscosity is that 0.64 polyethylene terephthalate isophthalic acid ester copolyester (copolymerization 10.0 moles of % M-phthalic acids) is 280 ℃ of fusions, carry out spinning with 1450m/ minute spinning speed, with gained not stretch yarn under 87 ℃, be stretched to 2.9 times, obtain boiling water shrinkage 15%, 55dtex/12 long filament (filament fiber number: heat-contractable ployester yarn 4.6dtex) (heat-contractable ployester multifilament textile Y ').
Use this polyester mutifilament yarn X ' and heat-contractable ployester multifilament textile Y ', make the mixed yarn of knitting of polyester with device shown in Figure 3.
That is, two polyester mutifilament yarn X ' and Y ' are drawn together, be supplied to the nozzle 3 that interweaves that is arranged between donor rollers 1 and the 1st carry-over pinch rolls (surface temperature is 120 ℃ a warm-up mill) 2, utilize 2.0kg/cm with 600m/ minute speed, 1.2% over feed rate(OFR) 2Compressed air interweave, the longitude and latitude of giving 65/m is staggered.Should illustrate that polyester mutifilament yarn X ' knits than being 62:38 with the mixed of polyester multifilament Y '.
Then, under the state of over feed rate(OFR) 1.2%, it directly in surface temperature circumvolution 8 times on 120 ℃ the warm-up mill 2 with strand, implement lax heat treatment, make the spontaneous stretching of polyester mutifilament yarn X ', after making polyester multifilament Y ' thermal contraction simultaneously, by being arranged at the slit heater 5 between warm-up mill 2 and the 2nd carry-over pinch rolls 4, under 230 ℃, implement the 2nd lax heat treatment in 0.05 second to carry out heat fixation with 1.8% over feed rate(OFR), after circumvolution on the 2nd carry-over pinch rolls (the cold roller) 42 times, in package 6, batch the mixed yarn of knitting as the 150dtex/84 long filament.
Mix the charging property of knitting yarn for gained, frictional electrification voltage is 900V.
Polyester mixes to be knitted in the manufacturing of yarn, does not see contacting of strand and slit heater 5, and broken end is to hammer into shape only 1 time in 1 day, per 1.
Gained mixed knit the plain cloth that yarn is made into 60/cm of warp thread, 35/cm of weft yarn, utilize well-established law under 135 ℃, to carry out dyeing in 60 minutes, dye black.For the quality of gained DYED FABRICS, be 1 grade, have high resilience simulate wool sense of touch, be to have to expand the spinning sample fabric of sense, Pi crack static does not take place when dress is used in addition.
[comparative example VI-1]
The single thread fiber number of polyester mutifilament yarn X is the 3.0dtex, to carry out in the same manner in making example VI-1.The gained DYED FABRICS is that quality is hard, and does not have the fabric (3 grades) of good sense of touch.
[comparative example VI-2]
Polyester mutifilament yarn X and polyester mutifilament yarn Y mixed knitted than being 50: 50 in making example VI-1, carries out in the same manner.The antistatic behaviour of gained DYED FABRICS is good, but quality is hard, is not good fabric (3 grades).
[comparative example VI-3]
Polyester mutifilament yarn X and polyester mutifilament yarn Y mixed knitted than being 90: 10 in making example VI-1, carries out in the same manner.The antistatic behaviour of gained DYED FABRICS is good, but because the contraction in the lax heat treatment is few, so polyester multifilament Y is not fully covered by polyester multifilament X institute, is not the fabric (1 grade) of good sense of touch.
[comparative example VI-4]
In polyester mutifilament yarn X in example VI-1, do not add the antistatic additive, carry out in the same manner.The quality of having used gained to mix the fabric of knitting yarn is 1 grade, and it is good to expand sense, high resilience, but does not have antistatic behaviour, generation Pi crack static when dress is used.
[comparative example VI-5]
The addition of poly (oxyalkylene) base system polyethers is 0.1 part, to carry out in the same manner in making example VI-1.
The quality of having used gained to mix the fabric of knitting yarn is 1 grade, and it is good to expand sense, high resilience, but does not have antistatic behaviour, generation Pi crack static when dress is used.
[comparative example VI-6]
In the example VI-1, the heat treatment that do not relax is made as the mixed yarn of knitting with common false twisting operation.It is many that gained mixes broken yarn, the fluffing of knitting yarn, the finished product rate variance.
(VII. the application the 4th inventive embodiment)
Elastic recovery rate (ER) during (30) 10% stretchings
According to JIS L 1013, specimen length is made as 25cm, first loading is made as under the state of every Denier load 1/30g, control fixing with air spider (air chuck) two ends.For condition determination, make draw speed be 20%/minute carry out 10% to stretch, then with return speed 20%/minute, remove loading on one side, Yi Bian loading point at the beginning of being back to.Measure number of times and carry out 3 times, ask its mean value.
Elongation * 100 when 10% elastic recovery rate when stretching=when stretching (10% elongation-residual elongation)/10% stretches
(31) stretching modulus of rigidity (EM)
Use constant speed stretching cupping machine and measure with the tape deck of its interlock.The length of sample is made as 25cm, first loading is made as under the state of every Denier load 1/30g, control two ends fixing with air spider.For condition determination, make draw speed be 20%/minute, partly draw tangent line by initial loading stress strain curve figure at trend curve, read 100% stress when stretching.Mensuration is carried out 5 times, asks its mean value.
Stress (g) * sample proportion/fiber number (Denier) when stretching modulus of rigidity (EM)=9 * 100 * 1% stretches
(32) thermal stress (TS) (under 160 ℃)
Use the thermal stress analyzer and measure with the tape deck of its interlock.With data (Capital material) use sampling jig to be made into the ring of 5cm.Then thermal stress analyzer and tape deck are prepared as the state that to measure at 20 ℃~300 ℃, the scope of stress 0~20g, the ring of sample 5cm of sampling is before hung on the hook of top, bottom of thermal stress analyzer, load after the first loading of every Denier 1/30g the mensuration of beginning thermal stress.Programming rate carried out with 300 ℃/120 seconds.Finish to measure in the moment that is warming up to 300 ℃.Mensuration is carried out 3 times.For thermal stress (160 ℃), read the stress g of 160 ℃ of points, and be scaled the stress of every 1dtex.
[example VII A-1]
(manufacturing of polyester A)
Implement in the same manner with the manufacture method of polyester A among the embodiment of polyester of organic system ultraviolet radiation absorption composition that has been copolymerization of copolyester B in the application the 1st invention, make polyester A.
(manufacturing of polyester B)
Implement in the same manner with the manufacture method of polyester B among the embodiment of polyester of organic system ultraviolet radiation absorption composition that has been copolymerization of copolyester B in the application the 1st invention, make polyester B.
(manufacturing of polyester mutifilament yarn X)
Throwingization is as described below carries out.With dry polymer each personal well-established law fusion in spinning equipment, be supplied to 2 composition composite spinning heads via gear pump.Core and sheath polymer ratio are set at the value of table 1 record.The molten polymer of core of Gong Geiing and sheath portion simultaneously, spinning nozzle from the circular composite spinning hole that is equipped with 72 nozzle bore 0.25mm, use cooling air to carry out cooling curing from common cross-current ejector half spinning tube, while giving the spinning oil boundling is a strand, speed with 3000m/min is drawn, and obtains the core-sheath-type polyester stretch yarn not of the 90dtex/72 long filament (single thread fiber number 1.25dtex) of birefringence 0.035.
Percentage elongation (ELA) is that 120%, 10% elastic recovery rate (ERA) when stretching is 30%, stretching modulus of rigidity (EMA) is 3.92GPa(400kg/mm 2), crystallization degree (XpA) is 40%, boiling water shrinkage (BWSA) is that thermal stress (TSA) under 1%, 160 ℃ is 0.26mN/dtex(30mg/dtex).
(manufacturing of polyester mutifilament yarn Y)
On the other hand, with copolymerization the inherent viscosity of 10 moles of % of M-phthalic acid (with 35 ℃ o-chlorphenol measured in solution) be that 0.64 polyethylene terephthalate is discharged from the spinning nozzle fusion, after making this discharge strand cooling curing, give finish, with after spinning fast 1200m/ minute and temporarily batching, under the condition of 85 ℃ of preheat roll temperature, 170 ℃ of heat setting heater (contact) temperature, 3.1 times of stretching ratios, draw speed 1200m/ minute, carry out, obtain the polyester complex fiber B(single thread fiber number 4.6dtex of 55dtex/12 long filament).The percentage elongation of polyester complex fiber B (ELB) is 30%, stretching modulus of rigidity (EMB) is 11.77GPa(1200kg/mm 2), boiling water shrinkage (BWSB) is that thermal stress (TSB) under 17%, 160 ℃ is for 4.4mN/dtex.
(mixing the manufacturing of knitting yarn)
With aforementioned antistatic polyester multifilament textile X, relax after the heat treatment with the condition of 110 ℃ of preheat roll temperature, 230 ℃ of heat setting heater (contactless) temperature, relaxation rate 2%, speed 600m/ minute, with aforementioned polyester mutifilament yarn Y doubling, mix and knit the formation composite yarn that interweaves with the air nozzle that interweaves, batch in winder, obtain the mixed yarn of knitting of 150dtex/84 long filament.The single thread fiber number of antistatic polyester composite fibre A is 1.2dtex.
Gained mixed knit yarn and be used for warp thread and weft yarn, woven be Habutae, according to well-established law enforcement refining, heat setting, dyeing, obtains not figuratum DYED FABRICS.Evaluation result is shown in table 3.
Should illustrate,, in the sense of utilizing skilled 5 people to pass judgment on is estimated, all be judged to be very good being designated as and be judged as good being designated as more than 1,3 people and be judged to be more than 2,3 people and bad be designated as 3, be divided into third-class level and mark for each assessment item of quality.
In addition,, fabric with the utensil of tubular insertion as Fig. 4, is placed weight on it, place after 3 hours, take off weight, the fold degree of placement in the time of 30 minutes marked by the benchmark of Table VII-1 as the restorative evaluation of fold.
[example VII A-2, comparative example VII-1~VII-4]
Except carrying out under the condition shown in the Table VII-2, use the method identical to carry out with example VII A-1.
[Table VII-1]
The state of fabric Level
There is not the yet not residual fold of any action 5
Residual fold then disappears but stretch 4
Even stretch also residual a little fold 3
Even stretch also a large amount of residual fold 2
Fold can't disappear fully and is acutely residual 1
[Table VII-2]
Figure 68465DEST_PATH_IMAGE008

Claims (21)

1. antistatic behaviour core-sheath-type polyester superfine fibre, its be core by polyester A, sheath portion by the core-sheath-type polyester complex fiber that copolyester B constitutes, it is characterized in that, satisfy following important document,
(i) the single thread fiber number is below the 1.5dtex,
The (ii) ratio A of the area A of core and the area B of sheath portion: B is 5: 95~80: 20 a scope,
(iii) single end strength is more than the 3.0cN/dtex,
(iv) the frictional electrification voltage of yarn is below the 2000V,
(v) polyester A is an antistatic polyester, in this antistatic polyester, with respect to aromatic polyester 100 weight portions, contain represented poly (oxyalkylene) base system polyethers 0.2~30 weight portion of (a) following general formula (1) and (b) be essentially non-reacted organic ion compound 0.05~10 weight portion as antistatic additive with this polyester
R 2O-(CH 2CH 2O)n(R 1O)m-R 2?(1)
In the formula, R 1Be alkylidene or the substituted alkylene of carbon number more than 2, R 2Be the monovalence alkyl of hydrogen atom, carbon number 1~40, the monovalence hydroxyl hydrocarbon of carbon number 2~40 or the monovalence acyl group of carbon number 2~40, n is the integer more than 1, and m is the integer more than 1.
2. the described antistatic behaviour core-sheath-type of claim 1 polyester superfine fibre, wherein, it is the polyester of the organic system ultraviolet radiation absorption composition of 0.1~5.0 weight % with respect to the polyester gross weight that copolyester B has been copolymerization.
3. the described antistatic behaviour core-sheath-type of claim 2 polyester superfine fibre, wherein, organic system ultraviolet radiation absorption composition is a benzo
Figure DEST_PATH_IMAGE001
Piperazine is an organic uv absorbers.
4. the described antistatic behaviour core-sheath-type of claim 1 polyester superfine fibre, wherein, it is the polyester of this metal organic sulfonate of 1.0~5.0 moles of % with respect to all acid composition except that metal organic sulfonate that copolyester B has been copolymerization.
5. the described antistatic behaviour core-sheath-type of claim 1 polyester superfine fibre, wherein, copolyester B has been copolymerization and has converted with phosphorus atoms with respect to the polyester gross weight and count 1,000~10, the polyester of the phosphorus flame retardant composition that the following general formula (2) of 000ppm is represented,
[changing 4]
Figure 672253DEST_PATH_IMAGE002
(2)
In the above-mentioned formula, R 1Be the hydroxy alkyl of hydrogen or carbon number 1~10, R 2Be the alkyl of hydrogen, carbon number 1~10 or the aryl of carbon number 6~24, R 3Alkyl or hydroxy alkyl for hydrogen, carbon number 1~10.
6. each described antistatic behaviour core-sheath-type polyester superfine fibre in the claim 1~5, wherein, the core-sheath-type polyester complex fiber has 3~8 fins from the outstanding laterally shape of fibre section central part in the cross section vertical with the single thread length direction, the projection coefficient of defined this fin of following formula is 0.3~0.7
The projection coefficient=(a1-b1)/a1
A1: from the length on inscribed circle center to the fin summit of the cross section inner surface vertical with fiber axis
B1: the inscribe radius of a circle of the cross section inner surface vertical with fiber axis.
7. each described antistatic behaviour core-sheath-type polyester superfine fibre in the claim 1~5, wherein, the core-sheath-type polyester complex fiber with the vertical cross section of single thread length direction in have the flat pattern that has engaged 3~6 circular section single thread at it on vertically, the maximum diameter α (major axis) of this flat pattern be 3~6 perpendicular to the represented flatness α/β of the ratio of the length β (minor axis) of the maximum diameter of this major axis.
8. cloth and silk is characterized in that, contains the described antistatic behaviour core-sheath-type of claim 1~7 polyester superfine fibre.
9. antistatic polyester composit false twisting processing yarn, its be 2 kinds of different polyester filament yarns of percentage elongation alternatively formed in the vertical the boundling portion that comprises mutual twist yarn shape coiling portion and the portion that interweaves, with open the polyester composit false twisting processing yarn that fine portion forms, it is characterized in that, satisfy the important document of following (i)~(iv)
(i) the polyester filament yarn X that percentage elongation is little is the core-sheath-type polyester complex fiber that core is made of copolyester B polyester A, sheath portion, and polyester A comprises antistatic polyester, in this antistatic polyester, with respect to aromatic polyester 100 weight portions, contain represented poly (oxyalkylene) base system polyethers 0.2~30 weight portion of (a) following general formula (1) and (b) be essentially non-reacted organic ion compound 0.05~10 weight portion as antistatic additive with this polyester
The polyester filament yarn Y that (ii) percentage elongation is big comprises polyester, and it is the delustering agent of 0~10wt% that this polyester contains with respect to aromatic polyester 100 weight portions,
(iii) be 2 layers of structure, wherein, polyester filament yarn X constitutes the core of composit false twisting yarn, and polyester filament yarn Y will batch around the core to mutual twist yarn shape constitutes outer portion (sheath portion),
(iv) the average yarn length of polyester filament yarn Y is longer by 5~20% than the average yarn of polyester filament yarn X,
R 2O-(CH 2CH 2O)n(R 1O)m-R 2?(1)
In the formula, R 1Be alkylidene or the substituted alkylene of carbon number more than 2, R 2Be the monovalence alkyl of hydrogen atom, carbon number 1~40, the monovalence hydroxyl hydrocarbon of carbon number 2~40 or the monovalence acyl group of carbon number 2~40, n is the integer more than 1, and m is the integer more than 1.
10. the described antistatic polyester composit false twisting of claim 9 processing yarn, its satisfy following (i)~(condition v),
(i) the frictional electrification voltage of antistatic polyester composit false twisting processing yarn is below the 2000V,
(ii) the ratio of the core area in the cross section vertical with fiber axis of polyester yarn X and sheath portion area is 5: 95~80: 20 a scope,
(iii) the intensity of antistatic polyester composit false twisting processing yarn is more than the 1.5cN/dtex,
(iv) the crimp percent of antistatic polyester composit false twisting processing yarn is 2~8%.
11. claim 9 or 10 described antistatic polyester composit false twisting processing yarns, wherein, the core-sheath-type polyester complex fiber has 3~8 fins from the outstanding laterally shape of fibre section central part in the cross section vertical with the single thread length direction, the projection coefficient of defined this fin of following formula is 0.3~0.7
The projection coefficient=(a1-b1)/a1
A1: from the length on inscribed circle center to the fin summit of the cross section inner surface vertical with fiber axis
B1: the inscribe radius of a circle of the cross section inner surface vertical with fiber axis.
12. claim 9 or 10 described antistatic polyester composit false twisting processing yarns, wherein, the core-sheath-type polyester complex fiber with the vertical cross section of single thread length direction in have the flat pattern that has engaged 3~6 circular section single thread at it on vertically, the maximum diameter α (major axis) of this flat pattern be 3~6 perpendicular to the represented flatness α/β of the ratio of the length β (minor axis) of the maximum diameter of this major axis.
13. cloth and silk is characterized in that, contains the described antistatic polyester composit false twisting of claim 9~12 processing yarn.
14. antistatic polyester mixes and to knit yarn, it is characterized in that, comprise antistatic polyester filament yarn X, with polyester filament yarn Y, and satisfy following (i)~(condition vi),
(i) antistatic polyester filament yarn X is the core-sheath-type polyester complex fiber that core is made of copolyester B polyester A, sheath portion, and polyester A comprises antistatic polyester, in this antistatic polyester, with respect to aromatic polyester 100 weight portions, contain represented poly (oxyalkylene) base system polyethers 0.2~30 weight portion of (a) following general formula (1) and (b) be essentially non-reacted organic ion compound 0.05~10 weight portion as antistatic additive with this polyester
(ii) the single thread fiber number of polyester filament yarn X is below the 1.5dtex,
(iii) mixing the frictional electrification voltage of knitting yarn is below the 2000V,
(iv) mix knit yarn be successively via air interweave operation, lax heat treatment step and,
(v) the mixed ratio of knitting of polyester filament yarn X and polyester filament yarn Y is 8: 2~6: 4,
(vi) polyester filament yarn X constitutes outer portion, the polyester filament yarn Y formation internal layer portion of knitting yarn of mixing,
R 2O-(CH 2CH 2O)n(R 1O)m-R 2?(1)
In the formula, R 1Be alkylidene or the substituted alkylene of carbon number more than 2, R 2Be the monovalence alkyl of hydrogen atom, carbon number 1~40, the monovalence hydroxyl hydrocarbon of carbon number 2~40 or the monovalence acyl group of carbon number 2~40, n is the integer more than 1, and m is the integer more than 1.
15. mixing, the described antistatic polyester of claim 14 knits yarn, wherein, the core-sheath-type polyester complex fiber has 3~8 fins from the outstanding laterally shape of fibre section central part in the cross section vertical with the single thread length direction, the projection coefficient of defined this fin of following formula is 0.3~0.7
The projection coefficient=(a1-b1)/a1
A1: from the length on inscribed circle center to the fin summit of the cross section inner surface vertical with fiber axis
B1: the inscribe radius of a circle of the cross section inner surface vertical with fiber axis.
16. mixing, the described antistatic polyester of claim 14 knits yarn, wherein, the core-sheath-type polyester complex fiber with the vertical cross section of single thread length direction in have the flat pattern that has engaged 3~6 circular section single thread at it on vertically, the maximum diameter α (major axis) of this flat pattern be 3~6 perpendicular to the represented flatness α/β of the ratio of the length β (minor axis) of the maximum diameter of this major axis.
17. cloth and silk is characterized in that, contains the mixed yarn of knitting of the described antistatic polyester of claim 14~16.
18. antistatic polyester mixes the manufacture method of knitting yarn, it is characterized in that, with percentage elongation (ELA) is more than 80%, elastic recovery rate (ERA) during 10% stretching is below 50%, stretching modulus of rigidity (EMA) is below the 5.89GPa, crystallization degree (XpA) is more than 25%, boiling water shrinkage (BWSA) is below 3%, thermal stress under 160 ℃ (TSA) is below the 0.44mN/dtex, and satisfy following (i)~the antistatic polyester filament yarn X ' of important document relax after the heat treatment, be below 40% with percentage elongation (ELB) again, stretching modulus of rigidity (EMB) is more than the 7.85GPa, boiling water shrinkage (BWSB) is more than 5%, thermal stress under 160 ℃ (TSB) is carried out doubling for the above polyester filament yarn Y ' of 0.88mN/dtex, so that the weight ratio of polyester mutifilament yarn X ' and polyester mutifilament yarn Y ' is 45/55~70/30, carry out interleaving treatment then
(i) the core-sheath-type polyester complex fiber that constitutes by copolyester B by polyester A, sheath portion for core of antistatic polyester multifilament textile X ', and polyester A comprises antistatic polyester, in this antistatic polyester, with respect to aromatic polyester 100 weight portions, contain represented poly (oxyalkylene) base system polyethers 0.2~30 weight portion of (a) following general formula (1) and (b) be essentially non-reacted organic ion compound 0.05~10 weight portion as antistatic additive with this polyester
(ii) the single thread fiber number of polyester mutifilament yarn X ' is below the 1.5dtex,
R 2O-(CH 2CH 2O)n(R 1O)m-R 2?(1)
In the formula, R 1Be alkylidene or the substituted alkylene of carbon number more than 2, R 2Be the monovalence alkyl of hydrogen atom, carbon number 1~40, the monovalence hydroxyl hydrocarbon of carbon number 2~40 or the monovalence acyl group of carbon number 2~40, n is the integer more than 1, and m is the integer more than 1.
19. the described antistatic polyester of claim 18 mixes the manufacture method of knitting yarn, wherein, the core-sheath-type polyester complex fiber has 3~8 fins from the outstanding laterally shape of fibre section central part in the cross section vertical with the single thread length direction, the projection coefficient of defined this fin of following formula is 0.3~0.7
The projection coefficient=(a1-b1)/a1
A1: from the length on inscribed circle center to the fin summit of the cross section inner surface vertical with fiber axis
B1: the inscribe radius of a circle of the cross section inner surface vertical with fiber axis.
20. the described antistatic polyester of claim 18 mixes the manufacture method of knitting yarn, wherein, the core-sheath-type polyester complex fiber with the vertical cross section of single thread length direction in have the flat pattern that has engaged 3~6 circular section single thread at it on vertically, the maximum diameter α (major axis) of this flat pattern be 3~6 perpendicular to the represented flatness α/β of the ratio of the length β (minor axis) of the maximum diameter of this major axis.
21. cloth and silk is characterized in that, contains the mixed yarn of knitting of antistatic polyester that is mixed the manufacture method manufacturing of knitting yarn by the described antistatic polyester of claim 18~20.
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Application publication date: 20111228