CN100346014C - Polyester fibers having deformed section - Google Patents

Polyester fibers having deformed section Download PDF

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Publication number
CN100346014C
CN100346014C CNB2003801101480A CN200380110148A CN100346014C CN 100346014 C CN100346014 C CN 100346014C CN B2003801101480 A CNB2003801101480 A CN B2003801101480A CN 200380110148 A CN200380110148 A CN 200380110148A CN 100346014 C CN100346014 C CN 100346014C
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section
polyester
fiber
polyester fibers
mentioned
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CN1761779A (en
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益田刚
神山三枝
水村知雄
宫坂信义
塚本亮二
服部启次郎
中岛卓
菊池胜志
逢坂浩幸
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Teijin Frontier Co Ltd
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Teijin Fibers Ltd
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    • 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
    • D01D5/253Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78Preparation processes
    • C08G63/82Preparation processes characterised by the catalyst used
    • C08G63/85Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • 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
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16Dicarboxylic acids and dihydroxy compounds
    • C08G63/18Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181Acids containing aromatic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • 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
    • Y10T428/2973Particular cross section
    • 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
    • Y10T428/2973Particular cross section
    • Y10T428/2975Tubular or cellular
    • 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
    • Y10T428/2973Particular cross section
    • Y10T428/2976Longitudinally varying
    • 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
    • Y10T428/2973Particular cross section
    • Y10T428/2978Surface characteristic

Abstract

Polyester fibers having a deformed section are produced from a polyester polymer which is obtained by polycondensing an aromatic dicarboxylate ester in the presence of a catalyst containing a mixture of a Ti component (A) comprising at least one a titanium alkoxide or a reaction product thereof with a specific carboxylic acid or its anhydride with a P compound component (B) represented by the following general formula (III) and/or a reaction product of a Ti compound component (C) with a P compound component (D) represented by the following general formula (IV). The obtained fibers have a favorable color tone and excellent qualities without showing fluffing.

Description

Polyester fibers having deformed section
Technical field
The present invention relates to polyester fibers having deformed section.In more detail, the present invention relates to use and have good color and be in harmonious proportion the polyester fibers having deformed section that the polyester polymers of excellent formability makes.
Background technology
Polyester polymers, particularly polyethylene terephthalate, PEN, polytrimethylene terephthalate and polybutylene terephthalate (PBT) have excellent machinery, physics, chemical property, thereby are widely used in fiber, film and other molded item field.
Described polyester polymers, for example polyethylene terephthalate can prepare by following method usually: glycol ester and/or its oligomer of preparation terephthalic acid (TPA), decompression heating in the presence of polymerization catalyst then makes the extremely predetermined degree of polymerization of its reaction.Other polyester also can be by preparing with above-mentioned same method.
Generally known: this moment the gained polyester quality be subjected to a great extent the polycondensation catalyst kind about, the polycondensation catalyst of widely used polyethylene terephthalate is an antimonial.
But, when using antimonial, polyester is carried out the long-time continuous melt-spun, to adhere to around the spinneret orifice and pile up foreign matter (being designated hereinafter simply as the spinnerets foreign matter), bending phenomenon occurs for molten polymer flow (bending), because of this reason, in spinning, stretching process, have fluff, problem such as fracture of wire or fibrous physical property are irregular.
Particularly when make fiber cross section by melt-spun be special-shaped fiber, spinneret orifice was complex-shaped, and above-mentioned spinnerets foreign matter has a significant impact the ejection state tool of molten polymer, will fluff in the spinning, problem such as fracture of wire.
For addressing these problems, people have proposed following method: use the catalyst (for example with reference to Japanese Patent Publication 59-46258 communique) of the product of titanium compound and trimellitic acid reaction formation as the preparation polyester; Use product that titanium compound and phosphite reactions form as the catalyst (for example with reference to Japanese kokai publication sho 58-38722 communique) for preparing polyester etc.These methods can improve the melting heat stability of polyester to a certain extent, but its raising effect is not enough, need in addition the tone of gained polyester polymers is improved.
In addition, the somebody proposes to use the catalyst (for example with reference to Japanese kokai publication hei 7-138354 communique) of the complex compound of titanium compound and phosphorus compound as the preparation polyester, though but use this method can improve melting heat stability to a certain extent, but its effect is insufficient, needs in addition the tone of gained polyester is improved.
Summary of the invention
First purpose of the present invention is to solve above-mentioned problems of the prior art, and a kind of high-quality polyester fibers having deformed section that has good tone, do not have fluffing is provided.This purpose is to realize by following polyester fibers having deformed section.
Polyester fibers having deformed section of the present invention is to contain polyester polymers as main component, has the polyester fiber of odd-shaped cross section, it is characterized in that:
Above-mentioned polyester polymers is formed by aromatic dicarboxylic acid ester's polycondensation in the presence of catalyst,
Above-mentioned catalyst contains at least a material that is selected from following mixture (1) and product (2),
Said mixture (1) is following compositions (A) and mixture (B):
(A) contain at least a being selected from (a) and titanium compound composition (A) (b),
(a) alkoxytitanium shown in the following general formula (I),
Figure C20038011014800071
[in the following formula (I), R 1, R 2, R 3And R 4Independent respectively expression is selected from a kind of of alkyl with 1-20 carbon atom and phenyl, and m represents the integer of 1-4, and m represents 2,3 or at 4 o'clock, 2,3 or 4 R 2And R 3Can be identical or different respectively.]
(b) product of aromatic polycarboxylic acid or its acid anhydrides shown in the alkoxytitanium of above-mentioned general formula (I) and the following general formula (II),
Figure C20038011014800081
[in the following formula (II), n represents the integer of 2-4];
(B) contain the phosphorus compound composition (B) of phosphorus compound shown at least a following general formula (III),
Figure C20038011014800082
[in the following formula (III), R 5, R 6And R 7Independent separately expression has the alkyl of 1-4 carbon atom, and X represents to be selected from-CH 2-Ji and-CH 2(Y) base (Y represents phenyl) is a kind of],
The mM value of contained titanium elements is M with the ratio (%) of above-mentioned aromatic dicarboxylic acid ester's mole numerical value in the above-mentioned titanium compound composition (A) Ti, the mM value of institute's phosphorus element-containing is M with the ratio (%) of above-mentioned aromatic dicarboxylic acid ester's mole numerical value in the phosphorus compound composition (B) P, the above-mentioned mixture of catalysts (1) that is used as is with M TiAnd M PSatisfying following formula (i) and combined amount (ii) uses:
1≤M P/M Ti≤15 (i)
10≤M P+M Ti≤100 (ii);
Above-mentioned product (2) is following compositions (C) and product (D):
(C) contain at least a titanium compound composition (C) that is selected from the compound of alkoxytitanium (c) shown in the general formula (I),
(D) contain the phosphorus compound composition (D) of phosphoric acid one Arrcostab shown at least a following general formula (IV),
Figure C20038011014800083
[in the following formula (IV), R 8Expression has the alkyl of 1-20 carbon atom or has the aryl of 6-20 carbon atom].
In the polyester fibers having deformed section of the present invention, for above-mentioned as mixture of catalysts (1) composition (A) and the composition (C) of above-mentioned product (2) as catalyst separately for, preferably alkoxytitanium (a) and alkoxytitanium (c) separately with the reaction mol ratio of the aromatic polycarboxylic acid of general formula (II) or its acid anhydrides 2: 1-2: in 5 scopes.
In the polyester fibers having deformed section of the present invention, above-mentioned reacting dose ratio as the composition (D) in the product (2) of catalyst and composition (C) is converted into the ratio (P/Ti) of the molar weight of contained titanium atom in the molar weight of contained phosphorus atoms in the composition (D) and the composition (C), preferably 1: 1-3: in 1 scope.
In the polyester fibers having deformed section of the present invention, preferred above-mentioned phosphorus compound as used general formula (IV) in the product (2) of catalyst is selected from phosphoric acid one Arrcostab.
In the polyester fibers having deformed section of the present invention, preferred above-mentioned aromatic dicarboxylic acid ester is in the presence of the catalyst of titanium-containing compound, and dialkyl and alkylene glycol ester by aromatic dicarboxylic acid carry out the diester that ester exchange reaction makes.
In the polyester fibers having deformed section of the present invention, preferred above-mentioned aromatic dicarboxylic acid is selected from terephthalic acid (TPA), 1,2-naphthalenedicarboxylic acid, phthalic acid, M-phthalic acid, diphenyl dicarboxylic acid and biphenoxyl ethane dioctyl phthalate, above-mentioned alkylene glycol is selected from ethylene glycol, butanediol, trimethylene glycol, 1, ammediol, neopentyl glycol, 1,6-hexylene glycol and 1, the 12-dodecanediol.
Second purpose of the present invention is on the basis of first purpose, and a kind of polyester fibers having deformed section is provided, can make not have with this fiber and stick together (ベ ト Star キ) sense, and the cloth and silk of soft feeling, barrier property, low-permeable, water imbibition, excellent in wear resistance.This purpose realizes by following polyester fibers having deformed section.
Promptly, a kind of polyester fibers having deformed section, this polyester fiber contains the polyester polymers of polycondensation formation in the presence of above-mentioned special catalyst as main component, and the shape of cross section of its single fiber is a flat pattern, and this flat pattern has the shape that 3-6 circular cross section is formed by connecting along long axis direction.
Preferred above-mentioned polyester fibers having deformed section contains the inorganic particle of 0.2-10% weight.
On the cross section of above-mentioned polyester fibers having deformed section, the flatness of representing with major axis width A and ratio A/B perpendicular to the Breadth Maximum B of the minor axis of this major axis is preferably 3-6.
On the cross section of above-mentioned polyester fibers having deformed section, the degree of profile of representing with the ratio B/C of the Breadth Maximum B of minor axis and minimum widith C (minimum widith of circular cross sectional shape connecting portion) is preferably greater than 1 and less than 5.
The 3rd purpose of the present invention is on the basis of first purpose, and the polyester fibers having deformed section of suction, rapid-drying properties excellence is provided.This purpose realizes by following polyester fibers having deformed section.
Promptly, a kind of polyester fibers having deformed section, this polyester fiber contains the polyester polymers of polycondensation formation in the presence of above-mentioned special catalyst as main component, have 3-8 on the cross section of its single fiber from the outstanding laterally wing portion of fiber section core, the projection coefficient that (iii) defines with following formula is 0.3-0.7.
Projection coefficient=(a 1-b 1)/a 1(iii)
[in the following formula, a 1Expression is by the inscribed circle center of the fibre section inwall length to wing portion summit, b 1The inscribed circle radius of expression fibre section inwall.]
The degree of crystallinity of preferred above-mentioned polyester fibers having deformed section is below 30%.
The boiling water shrinkage of preferred polyester fibers having deformed section is 15-70%.
The 4th purpose of the present invention is on the basis of first purpose, and a kind of polyester fibers having deformed section is provided, and can make the cloth and silk of the liquor style with bulk softness with this polyester fiber.This purpose realizes by following polyester fibers having deformed section.
Promptly, a kind of polyester fibers having deformed section, this polyester fiber contains the polyester polymers of polycondensation formation in the presence of above-mentioned special catalyst as main component, the cross section of its single fiber is by core and be radial outstanding a plurality of wing portion along the length direction of this core from core and constitute, and by to satisfy simultaneously following formula (iv)-(polyester fiber vi) carries out the alkali decrement treatment, at least a portion that makes wing portion from core segment from.
1/20≤S B/S A≤1/3 (iv)
0.6≤L B/D A≤3.0 (v)
W B/D A≤1/4 (vi)
(S AThe cross-sectional area of expression core; D AIts circumscribed diameter when representing the diameter when the core cross section is circular or being not circle; S B, L BAnd W BCross-sectional area, maximum length and the Breadth Maximum of representing wing portion respectively.)
It is that (χ of parameter of consistency vii) is the compound of 0.1-2.0 for the following formula of 0.5-5.0% weight that preferred above-mentioned polyester fibers having deformed section contained before alkali treatment with respect to polyester fiber weight.
χ=(V a/RT)(δa-δb) 2 (vii)
(V aMolal volume (the cm of expression polyester 3/ mol), R represents gas constant (J/molK), and T represents absolute temperature (K), and δ a and δ b represent the solubility parameter (J of polyester and compound respectively 1/2/ cm 3/2).)
The 5th purpose of the present invention is on the basis of first purpose, a kind of polyester fibers having deformed section is provided, can make with this polyester fiber and to have rough harsh feeling (キ シ ミ sense), loftiness, flexibility, light weight sense excellence, and do not have the cloth and silk of the silk style of uneven dyeing.This purpose realizes by following polyester fibers having deformed section.
Promptly, a kind of polyester fibers having deformed section, this polyester fiber contains the polyester polymers of polycondensation formation in the presence of above-mentioned special catalyst as main component, the shape of cross section of its single fiber is to be made of gable and the protuberance that extends out from this leg-of-mutton summit, satisfy following formula simultaneously and (viii) and (ix), have the hollow space of 3-15% in this gable.
0.7≤L1/L2≤3.0 (viii)
3.0≤h2/h1≤10.0 (ix)
(L1 represents the distance from the tie point of gable and protuberance to the protuberance other end, L2 represents that tie point from gable and protuberance is to the distance the gable opposite side relative with this tie point, h1 represents the width of protuberance, h2 represent the gable relative with the tie point of gable and protuberance to edge lengths.)
It is metal organic sulfonate shown in the following general formula (V) of 0.5-2.5% weight that preferred above-mentioned polyester fibers having deformed section contains with respect to this polyester fiber weight.
R 9SO 3M (V)
(R 9The expression carbon number is the alkyl of 3-30 or aryl or the alkylaryl that carbon number is 7-40, and M represents alkali metal or alkaline-earth metal.)
The accompanying drawing summary
Fig. 1 is the ideograph of the shape of cross section example of the expression polyester fibers having deformed section of realizing the present invention's second purpose.
Fig. 2 represents to realize the example of shape of cross section of the polyester fibers having deformed section of the present invention's second purpose, is used for each size is described.
Fig. 3 is the ideograph of the shape of cross section example of an expression polyester fibers having deformed section realizing the 3rd purpose.
Fig. 4 is the ideograph of the spinning jet used spinneret orifice example of the polyester fibers having deformed section spinning of expression realization the present invention the 3rd purpose.
Fig. 5 is the ideograph of the shape of cross section example of the preceding polyester fibers having deformed section of the alkali decrement treatment of expression realization the present invention the 4th purpose.
Fig. 6 is the ideograph of the spinning jet used spinneret orifice example of the polyester fibers having deformed section spinning of expression realization the present invention the 4th purpose.
Fig. 7 represents to realize an example of the side view of the present invention's the 4th purpose (after the alkali decrement treatment) polyester fibers having deformed section.
Fig. 8 represents to realize the example of shape of cross section of the polyester fibers having deformed section of the present invention's the 5th purpose, is used for each size is described.
Fig. 9 is the ideograph of the spinning jet used spinneret orifice example of the polyester fibers having deformed section spinning of expression realization the present invention the 5th purpose.
The best mode that carries out an invention
Polyester fibers having deformed section of the present invention be contain polyester polymers as principal component, have the polyester fiber of odd-shaped cross section.Key is that this polyester polymers is obtained by aromatic dicarboxylic acid ester's polycondensation in the presence of following special catalyst.Thus, not only can obtain having the product that spinnerets spinning that good tone and use have complicated spinneret orifice forms, and can make the not high-quality polyester fibers having deformed section of fluffing.And, therefore can stably make or even the profiled fibre of height heteromorphosis with above-mentioned polymer, adopt this fiber can give full play to function (water imbibition, soil resistance, non-permeability etc.) and liquor style (feel, tone variations, gloss etc.) because of heteromorphosis obtains.Above-mentioned odd-shaped cross section is meant the cross sectional shape beyond the circular cross-section, refers to ellipse, flat, triangle, four jiaos, cross, star, C shape, H shape, I shape, L shaped, S shape, T shape, U-shaped, V-arrangement, W shape, X-shaped, Y shape, Z-shaped uiform section.The cross sectional shape that the present invention has strict demand to the angle and the size of each several part on complex cross-sectional shape, the pair cross-section, its effect is more remarkable.
Above-mentioned polycondensation contains at least a material that is selected from mixture (1) and product (2) with catalyst, described mixture (1) is the mixture of following titanium compound composition (A) and phosphorus compound composition (B), and described product (2) is the product of following titanium compound composition (C) and phosphorus compound composition (D).
Contain at least a being selected from (a) and composition (b) as the titanium compound (A) in the mixture (1) of polycondensation catalyst,
(a) alkoxytitanium shown in the following general formula (I),
Figure C20038011014800131
[in the following formula (I), R 1, R 2, R 3And R 4Independent respectively expression be selected from has 1-20, the alkyl of preferred 1-6 carbon atom and phenyl a kind of, m represents 1-4, the preferred integer of 2-4, m represents integer 2,3 or, 2,3 or 4 R at 4 o'clock 2And R 3Can be identical or different respectively.]
(b) product of aromatic polycarboxylic acid or its acid anhydrides shown in the alkoxytitanium of above-mentioned general formula (I) and the following general formula (II),
Figure C20038011014800132
[in the following formula (II), n represents integer 2-4, preferred 3-4].
Contain phosphorus compound shown at least a following general formula (III) as the phosphorus compound (B) in the mixture (1) of polycondensation catalyst,
Figure C20038011014800141
[in the following formula (III), R 5, R 6And R 7Independent separately expression has the alkyl of 1-4 carbon atom, and X represents to be selected from-CH 2-Ji and-CH 2(Y) (Y represents phenyl) is a kind of].
Product (2) as polycondensation catalyst is the product of titanium compound composition (C) and phosphorus compound composition (D).
Above-mentioned titanium compound composition (C) contains at least a following (c) and the composition (d) of being selected from,
(c) alkoxytitanium shown in the above-mentioned general formula (I) and
(d) product of aromatic polycarboxylic acid or its acid anhydrides shown in the alkoxytitanium of above-mentioned general formula (I) and the above-mentioned general formula (II).
Above-mentioned phosphorus compound composition (D) contains phosphorus compound shown at least a following general formula (IV),
Figure C20038011014800142
[in the following formula (IV), R 8Expression has the alkyl of 1-20 carbon atom or has the aryl of 6-20 carbon atom, and p represents 1 or 2 integer].
The mixture (1) that uses above-mentioned titanium compound composition (A) and above-mentioned phosphorus compound composition (B) is during as polycondensation catalyst, dissolubility and the compatibility height of product (b) in polyester polymers as aromatic carboxylic acid shown in alkoxytitanium (a) shown in the general formula (I) of titanium compound composition (A) and this alkoxytitanium (a) and the general formula (II) or its acid anhydrides, even therefore residual in the polyester polymers that obtains by polycondensation have a titanium compound composition (A), when its melt spinning, foreign matter can not take place the spinning spinneret periphery yet piles up, thereby can be with the good polyester filament of high spinning efficient spinning quality.
As used among the present invention, preferably use tetraisopropoxy titanium, four titanium propanolates, four titanium n-butoxide, purity titanium tetraethoxide, four phenoxide titaniums, three metatitanic acids, eight Arrcostabs and two metatitanic acids, six Arrcostabs etc. as the titanium compound composition (A) of polycondensation catalyst or (C) alkoxytitanium (a) shown in the used general formula (I).
Aromatic polycarboxylic acid or its acid anhydrides shown in the general formula (II) of reaction are preferably selected from phthalic acid, trimellitic acid, benzene-1,2,3-tricarboxylic acid, pyromellitic acid and their acid anhydrides with alkoxytitanium (a) or (c).When particularly using trimellitic anhydride, the product that obtains demonstrates high-affinity to polyester polymers, can effectively prevent above-mentioned foreign matter accumulation.
Make above-mentioned titanium compound composition (A) or (C) in used alkoxytitanium (a) or (c) and when aromatic polycarboxylic acid shown in the general formula (II) or its anhydride reaction, for example preferably aromatic polycarboxylic acid or its acid anhydrides are dissolved in the solvent, drip alkoxytitanium (a) or (c) in this mixed liquor, heating is at least 30 minutes under 0-200 ℃ temperature.Above-mentioned solvent is selected in the ammediol, 1,4-butanediol, benzene and dimethylbenzene etc. preferably as required from ethanol, ethylene glycol, 1.
Here, to alkoxytitanium (a) or (c) and the reaction mol ratio of aromatic polycarboxylic acid shown in the general formula (II) or its acid anhydrides be not particularly limited, if the ratio of alkoxytitanium is too high, then the situation of tone variation, softening point reduction can appear in the gained polyester, otherwise if the ratio of alkoxytitanium is low excessively, then polycondensation reaction is difficult to carry out.Therefore, preferred alkoxytitanium (a) or (c) and the reaction mol ratio of aromatic polycarboxylic acid shown in the general formula (II) or its acid anhydrides be in the scope of (2: 1)-(2: 5).
The product (b) that is obtained by this reaction or (d) can like this directly use also can be used it with the be recrystallized back of purifying such as acetone, methyl alcohol and/or ethyl acetate.
Among the present invention, be preferably selected from the dimethyl ester, diethylester class, dipropyl class, dibutyl ester class of phosphonate derivatives such as methoxycarbonyl group methane phosphonic acid, carbethoxyl group methane phosphonic acid, the third oxygen carbonyl methane phosphonic acid, butoxy carbonyl methane phosphonic acid, methoxycarbonyl group phenyl methane phosphonic acid, carbethoxy phenyl methane phosphonic acid, the third oxygen carbonyl phenyl methane phosphonic acid and butoxy carbonyl phenyl methane phosphonic acid etc. as phosphorus compound (phosphonate compound) shown in the used general formula (III) of the phosphorus compound composition (B) in the mixture (1) of polycondensation catalyst.
When the phosphorus compound composition (B) that will contain the phosphorus compound (phosphonate compound) of general formula (III) is used for aromatic dicarboxylic acid ester's polycondensation reaction, compare with the phosphorus compound that is used as reaction stabilizer usually, the reaction of itself and titanium compound composition (A) is carried out relatively gentlely, thereby the catalyst activity longer duration of the titanium compound composition (A) in the polycondensation process, thereby can reduce the amount ratio of titanium compound composition (A) with respect to the amount of the aromatic dicarboxylic acid ester in the polycondensation reaction system.And in the polycondensation reaction system that comprises the phosphorus compound composition (B) that contains phosphorus compound shown in the general formula (III),, can not reduce the heat endurance of gained polyester polymers, and can not make its tone variation even add a large amount of stabilizing agents yet yet.
Among the present invention, when using mixture (1), if the ratio (%) of the mM value of contained titanium elements and above-mentioned aromatic dicarboxylic acid ester's mole numerical value is M in the above-mentioned titanium compound composition (A) as polycondensation catalyst Ti, the mM value of institute's phosphorus element-containing is M with the ratio (%) of above-mentioned aromatic dicarboxylic acid ester's mole numerical value in the phosphorus compound composition (B) P, then with M TiAnd M PSatisfy following relational expression (i) and combined amount (ii) and use mixture (1):
1≤M P/M Ti≤15 (i)
10≤M P+M Ti≤100 (ii)。
Compare M p/ M TiBe more than 1 below 15, be preferably more than 2 below 10.If than M p/ M TiLess than 1, then the form and aspect of gained polyester polymers may yellowing, and if this ratio surpasses 15, then the polycondensation reaction of the polycondensation catalyst that constitutes thus is abundant inadequately, is difficult to obtain the target polyesters polymer.The M that compares of the present invention p/ M TiScope narrower than traditional Ti-P series catalysts, but by setting such scope for, can obtain with traditional Ti-P series catalysts the excellent effect that can't obtain.
(M P+ M T) and value be more than 10 below 100, be preferably more than 20 below 70.(M P+ M Ti) value was less than 10 o'clock, the fibre forming property of gained polyester polymers is not enough, and the production efficiency in the melt-spun operation does not reach requirement, and the performance of gained fiber is good inadequately.And if (M P+ M Ti) value is above 100, when then the gained polyester polymers being carried out melt-spun, spinnerets will be piled up foreign matter on every side, though be small pile-up.Usually preferred M TiValue be 2-15, more preferably 3-10.
Among the present invention, when using above-mentioned product (2) as polycondensation catalyst, the phosphorus compound of the general formula (IV) that phosphorus compound composition (D) is used for example can be following compound: phosphoric acid one alkyl esters, for example oneself ester of phosphoric acid one positive butyl ester, phosphoric acid, phosphoric acid one (dodecyl) ester, phosphoric acid one lauryl and phosphoric acid one oil base ester etc.; Phosphoric acid one aryl ester class, for example phosphoric acid one phenylester, phosphoric acid one benzyl ester, phosphoric acid one (4-ethylphenyl) ester, phosphoric acid one biphenyl ester, phosphoric acid one naphthyl ester and phosphoric acid one anthryl ester etc.; Phosphate dialkyl ester class, for example diethyl phosphate, di(2-ethylhexyl)phosphate propyl ester, dibutylphosphoric acid ester, di(2-ethylhexyl)phosphate lauryl and di(2-ethylhexyl)phosphate oil base ester etc.; And di(2-ethylhexyl)phosphate aryl ester class, for example di(2-ethylhexyl)phosphate phenylester etc.Wherein, preferably using n in the above-mentioned formula (V) is 1 o'clock phosphoric acid one Arrcostab or phosphoric acid one aryl ester.
Used phosphorus compound composition (D) can be the mixture of the phosphorus compound of two or more general formulas (IV) among the present invention, and for example the mixture of the mixture of phosphoric acid one Arrcostab and phosphate dialkyl ester, phosphoric acid one phenyl ester and diphenyl phosphate is preferred combination.Be benchmark with whole mixture gross masses especially preferably, phosphoric acid one Arrcostab accounts for more than 50% in the mixture, particularly accounts for the composition more than 90%.
The method for preparing the product of above-mentioned titanium compound composition (C) and above-mentioned phosphorus compound composition (D) for example can be with two kinds of compositions (C) and (D) mixing, heats to be prepared in glycol.That is, if the glycol solution that contains titanium compound composition (C) and phosphorus compound composition (D) is heated, then glycol solution will become muddy, and the product of two kinds of compositions (C), (D) is separated out as precipitation.Can collect this precipitation, as the catalyst that is used to prepare polyester polymers.
As operable glycol herein, the preferred identical composition of diol component that uses the polyester that makes with the gained catalyst with formation.For example, when polyester is polyethylene terephthalate, preferably make spent glycol; When polyester is the poly terephthalic acid propylene glycol, preferably use 1, ammediol; When polyester is polybutylene terephthalate (PBT), preferably use 1, the 4-butanediol.
Product (2) as polycondensation catalyst of the present invention can be prepared as follows: titanium compound composition (C) is mixed simultaneously with phosphorus compound composition (D) and glycol three, it is heated, can make.But because be to make titanium compound composition (C) and phosphorus compound composition (D) reaction by heating, the product that is insoluble to glycol is separated out as precipitation, carries out so preferred precipitation is separated out reaction homogeneous before.Therefore, in order effectively to obtain reaction precipitation, preferably by preparing titanium compound composition (C) and phosphorus compound composition (D) glycol solution separately in advance, the method with these solution mixing and heating is prepared then.
Composition (C) and reaction temperature (D) are preferably 50 ℃-200 ℃, and the reaction time was preferably 1 minute-4 hours.If it is low that reaction temperature is spent, then reaction becomes insufficient, perhaps reacts required time and increases, thereby can't effectively obtain reaction precipitation by the reaction of homogeneous.
About the titanium compound composition (C) that adds thermal response in the glycol blending ratio with phosphorus compound composition (D), the molar ratio of phosphorus atoms and titanium atom is preferably 1.0-3.0, more preferably 1.5-2.5.If blending ratio is in above-mentioned scope, phosphorus compound composition (D) and titanium compound composition (C) complete reaction roughly then, there is not the not reactant of complete reaction, even thereby directly use this product, the form and aspect of gained polyester polymers also are good, and have excessive unreacted phosphorus compound (V) hardly, so can not hinder the polyester reactivity, the production efficiency height.
The polycondensation catalyst that uses among the present invention preferably contains compound shown in the following general formula (VI) with product (2).
(the R in the formula (VI) 10And R 11Independently represent a kind of following group that is selected from separately: come from the R in the general formula (I) of representing the used alkoxytitanium of above-mentioned titanium compound composition (C) 1, R 2, R 3, R 4R with the general formula (IV) of representing the used phosphorus compound of above-mentioned phosphorus compound composition (D) 8, and have the aryl of 6-12 carbon atom.)
Titanium compound shown in the formula (VI) and phosphorus compound (III) or product (IV) have high catalyst activity, so have good color tone (low b value) with its polyester polymers that makes, the content of acetaldehyde, kish and cyclic trimer is enough low on reality is used, and has sufficient polymer performance in actual applications.The content of product is more than 50% quality shown in preferred this formula (VI), more preferably more than 70% quality.
In the presence of above-mentioned product (2), during the polycondensation aromatic dicarboxylic acid ester, needn't separate the product precipitation (2) and the glycol that as above obtain, can be with it directly as the catalyst for preparing polyester polymers.Also can from the glycol solution that contains product precipitation (2), isolate sediment by means such as centrifugation processing or filtrations, then with this product precipitation (2) with for example recrystallization agent such as acetone, methyl alcohol and/or the water purification that is recrystallized, then this purifying thing is used as described catalyst.The chemical constitution of this catalyst can be confirmed by the metal quantitative analysis of solid NMR and XMA.
Polyester polymers used among the present invention can obtain by polycondensation aromatic dicarboxylic acid ester in the presence of catalyst, and wherein said catalyst contains above-mentioned titanium compound composition (A) and phosphorus compound (phosphonate compound) mixture (1) (B) and/or the product (2) of titanium compound composition (C) and phosphorus compound composition (D).Among the present invention, preferred aromatic dicarboxylic acid ester is the diester that aromatic dicarboxylic acid composition and aliphatic dihydric alcohol composition form.
Here said aromatic dicarboxylic acid composition preferably is main component with the terephthalic acid (TPA).More particularly, be benchmark with the content of whole aromatic dicarboxylic acid compositions, preferred terephthalic acid (TPA) accounts for more than 70% mole.Here, the preferred aromatic dicarboxylic acids beyond the terephthalic acid (TPA) for example has phthalic acid, M-phthalic acid, naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, biphenoxyl ethane dioctyl phthalate etc.
On the other hand, the preferred aliphatic series glycol component contains alkylene glycol, for example can make spent glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexylene glycol and 1,12-dodecanediol, preferred especially ethylene glycol.
Among the present invention, the preferred polyester polymer is to be the polyester of main repetitive with terephthalic acid (TPA) and the formed ethylene glycol terephthalate of ethylene glycol.Here, be meant that the amount with whole repetitives in the polyester is a benchmark, above-mentioned ethylene glycol terephthalate repetitive accounts for more than 70% mole.
Used polyester polymers also can be the copolyester that is formed by sour composition that constitutes polyester or diol component copolymerization among the present invention.
As the co-poly carboxylic acid composition, except that can using above-mentioned aromatic dicarboxylic acid, can also use aliphatic dicarboxylic acids such as adipic acid, decanedioic acid, azelaic acid, decane dicarboxylic acid; Cyclohexyl dicarboxylic acid waits difunctionality carboxylic acid composition such as ester ring type dicarboxylic acids or its to become ester derivant as raw material.The copolymerization diol component can also use ester ring type glycol such as cyclohexanedimethanol except that can using above-mentioned aliphatic diol; Bis-phenol, hydroquinones, 2, aromatic diols such as 2-two (4-beta-hydroxy ethoxyl phenenyl) propane class etc. are as raw material.
And, also can use the copolyester polymer that obtains as the copolymer composition copolymerization with multi-functional compounds such as trimesic acid, trimethylolethane, trimethylolpropane, Pehanorm, pentaerythrites.
Above-mentioned polyester polymers and copolyester polymer can be used alone, and also can be used in combination of two or more.
Among the present invention, polyester polymers preferably uses the aromatic dicarboxylic acid ester's of above-mentioned aromatic dicarboxylic acid and aliphatic diol formation polycondensation product.This aromatic dicarboxylic acid ester can also can prepare by the dialkyl of aromatic dicarboxylic acid and the ester exchange reaction of aliphatic diol by two esterification prepared in reaction of aromatic dicarboxylic acid and aliphatic diol.Just, employing is the method for raw material via ester exchange reaction with the dialkyl of aromatic dicarboxylic acid, with be that the method that raw material carries out two esterifications reactions is compared with the aromatic dicarboxylic acid, have less this benefit of dispersing of the phosphorus compound that adds as the phosphorus stabilizer agent in the polycondensation reaction.
And, preferably before beginning, ester exchange reaction adds a part and/or whole titanium compound compositions (A) or (C) of amount, it is used as catalyst for ester exchange reaction and two catalyst for reaction of polycondensation catalyst.Do like this, can reduce the titanium compound content in the final gained polyester.For example the situation of polyethylene terephthalate is carried out more specific description, preferably carry out in the presence of titanium compound composition (A) based on the dialkyl of the aromatic dicarboxylic acid of terephthalic acid (TPA) and the ester exchange reaction of ethylene glycol, wherein said titanium compound composition (A) contains at least a composition that is selected from the product (b) of aromatic polycarboxylic acid shown in alkoxytitanium shown in alkoxytitanium (a) shown in the above-mentioned general formula (I), the above-mentioned general formula (I) and the above-mentioned general formula (II) or its acid anhydrides.In the reactant mixture of the diester that contains aromatic dicarboxylic acid and ethylene glycol that obtains by this ester exchange reaction, further add phosphorus compound (phosphonate compound) shown in the above-mentioned general formula (III), perhaps add the product of titanium compound composition (C) and above-mentioned phosphorus compound composition (D), in the presence of these compositions, carry out polycondensation.
When carrying out above-mentioned ester exchange reaction, usually under normal pressure, implement, if but depress enforcement in adding of 0.05-0.20MPa, then can further promote the reaction that the catalyst action by titanium compound composition (A) carries out, and the accessory substance diethylene glycol (DEG) can not produce in a large number, thereby characteristic such as heat endurance can be better.Temperature is preferably 160-260 ℃.
Among the present invention, when aromatic dicarboxylic acid is terephthalic acid (TPA), can use terephthalic acid (TPA) and dimethyl terephthalate (DMT) initiation material as polyester.In this case, can use the polyalkylene terephthalates diol ester is carried out depolymerization and recovery dimethyl terephthalate (DMT) that obtains or the recovery terephthalic acid (TPA) that its hydrolysis is obtained.In this case, consider recycled polyesters such as the PET bottle that preferred especially use is reclaimed, fiber product, polyester film product from the resources effective utilization.
Polycondensation reaction can be carried out with a groove, also can divide a plurality of grooves to carry out.Can prepare polyester of the present invention like this, the polyester that obtains in the condensation polymerization step is extruded with molten condition usually,, granulate then (section shape) simultaneously with its cooling.
The used polyester of the present invention who obtains in the above-mentioned condensation polymerization step further can be carried out solid phase polycondensation as required.
This solid phase polycondensation step comprises a step at least, under the pressure condition of 190-230 ℃ temperature, 1kPa-200kPa, carries out under inert atmospheres such as nitrogen, argon gas, carbon dioxide.
As required, make the granular polyester that obtains via such solid phase polycondensation step and water, steam, contain the inert gas of steam, the air etc. that contains steam contacts, and implements water treatment, makes catalysqt deactivation contained in the section thus.
Comprise as mentioned above esterif iotacation step and condensation polymerization step polyester manufacture technology can with in batches, semicontinuous, continuous any form carries out.
The preferred used polyester polymers of the present invention is selected from polyethylene terephthalate, polytrimethylene terephthalate and polybutylene terephthalate (PBT).
With L *a *b *Color table colour system (JIS Z 8729) is a benchmark, and the preferred used polyester polymers of the present invention has the L of 77-85 *The b of value and 2-5 *Value.
The inherent viscosity of the used polyester of the present invention that makes like this is preferably 0.40-0.80, and 0.45-0.75 more preferably is preferably the scope of 0.50-0.70 especially.If inherent viscosity is less than 0.40, the insufficient strength of fiber then.And inherent viscosity surpasses 0.80, then needs the inherent viscosity of excessive raising raw polymer, and this is uneconomical.
Polyester used among the present invention can contain minor amounts of additives as required, for example antioxidant, ultra-violet absorber, fire retardant, fluorescent whitening agent, delustering agent, positive toner, defoamer, antistatic additive, antiseptic, light stabilizer, heat stabilizer, opacifier, especially preferably add titanium dioxide as delustering agent, add antioxidant as stabilizing agent.
Preferred above-mentioned titanium dioxide has the average grain diameter of 0.01-2 μ m, and preferably its content in polyester polymers is the 0.01-10% quality.
In addition, the content of contained titanium from above-mentioned catalyst in the polyester polymers does not comprise as delustering agent and adds titanium in the titanium dioxide of coming in.
When the titanium dioxide that contains in the polyester polymers as delustering agent, can only remove TITANIUM DIOXIDE DELUSTRANT from the polyester polymers test portion that is used for measuring by following operation: this polyester polymers test portion is dissolved in the hexafluoroisopropanol, this solution is carried out centrifugation, make titanium dioxide granule precipitation separation from above-mentioned solution, by decanting process separated and collected supernatant, the solvent in this recovery component is removed in evaporation, makes and treats test agent.
Above-mentioned antioxidant preferably uses the antioxidant of Hinered phenols.The addition of antioxidant is preferably below 1% quality, more preferably the 0.005-0.5% quality.If this addition surpasses 1% quality, then its effect is saturated, and the reason of formation scum silica frost will become melt-spun the time.Can be used in combination the anti-secondary oxidation agent of hindered phenol anti-oxidants and thioether class.
The method that above-mentioned antioxidant is added in the polyester is not particularly limited, can adds in any stage between ester exchange reaction begins to finish to polycondensation reaction.
The polyester fibers having deformed section of second purpose of the present invention is on the basis of first purpose, realize by polyester fibers having deformed section as described below, can make not have with this fiber and stick together sense, and the cloth and silk of soft feeling, barrier property, low-permeable, water imbibition, excellent in wear resistance.
Promptly, a kind of polyester fibers having deformed section, this polyester fiber contains the polyester polymers of polycondensation formation in the presence of above-mentioned special catalyst as main component, and fiber cross section is shaped as flat pattern, and this flat pattern has the shape that 3-6 circular cross section is formed by connecting along its length.
Here, " being formed by connecting " is not that expression is actual in its melt-spun stage connection, and is meant that the result has " being formed by connecting " shape.Here, " circular cross section " not only comprises circle, also comprises ellipse.
The shape of above-mentioned fiber cross section as shown in Figure 1.Fig. 1 (a)-(f) is the figure of this fiber cross section shape of modal representation, (a) 3 shapes that circular cross section is formed by connecting of expression, (b) 4 shapes that circular cross section is formed by connecting of expression, (c) 5 shapes that circular cross section is formed by connecting of expression.
Promptly, the shape of above-mentioned fiber cross section is circular cross section (long axis direction) shape of being formed by connecting along its length, be that protuberance and protuberance (peak and peak), recess and recess (Gu Yugu) they are the shape that overlaps and form axisymmetrically with major axis, as mentioned above, and the preferred 3-6 of the number of circular cross section.When the number of circular cross section was 2, the cloth and silk of circular cross-section fiber was soft, had the tendency of barrier property, low-permeable, water imbibition reduction.And the number of circular cross section surpasses 7, and then fiber easily breaks, and has the tendency that mar proof reduces.
Preferred above-mentioned polyester fibers having deformed section contains the inorganic particle of 0.2-10% weight, because this can further improve barrier property.
Describe with Fig. 2 below.For above-mentioned polyester fibers having deformed section, the flatness of representing with the major axis width A of fiber cross section and ratio A/B perpendicular to the Breadth Maximum B of the minor axis of this major axis is preferably 3-6.Less than 3 o'clock, have the soft feeling downward trend, and, the trend of sticking together sense that produces is arranged then greater than 6 o'clock, thereby not preferred.
In addition, for above-mentioned polyester fibers having deformed section, never stick together sense, improve absorptive angle and set out, preferably the degree of profile of representing with the ratio B/C of the Breadth Maximum B of the minor axis of flattened cross-sectional and minimum widith C (minimum widith of circular cross section connecting portion) is 1<B/C<5.That is, the recess of flat cross section fiber of the present invention is owing to capillarity makes moisture diffusion, can obtain excellent water absorbing properties thereby compare with the circular cross-section fiber, but degree of profile is, only becomes flat fiber, produces to stick together sense, does not also have water imbibition at 1 o'clock.B/C is 5 when above, though do not stick together sense, also has water imbibition, but the connecting portion of circular cross section is too short, and the intensity decreases of flat cross section fiber can produce the cross section and easily break and wait other defective, thereby preferred B/C satisfies 1<B/C<5, more preferably satisfied 1.1<B/C<2.
The total fiber number of the polyester fibers having deformed section that constitutes to the single fiber fiber number of above-mentioned polyester fibers having deformed section and by this single fiber does not have special provision, when being used for the dress material purposes, preferred single fiber fiber number is 0.3-3.0dtex, and the total fiber number of polyester fibers having deformed section is preferably 30-200dtex.
The 3rd purpose of the present invention is on the basis of first purpose, and the polyester fibers having deformed section of suction, rapid-drying properties excellence is provided.This purpose realizes by following polyester fibers having deformed section.
Promptly, a kind of polyester fibers having deformed section, this polyester fiber contains the polyester polymers of polycondensation formation in the presence of above-mentioned special catalyst as main component, fiber cross section is made of core and 3-8 wing portion of giving prominence to laterally from core, and the projection coefficient that (iii) defines with following formula is 0.3-0.7.
Projection coefficient=(a 1-b 1)/a 1(iii)
[in the following formula, a 1Expression is by the inscribed circle center of the fibre section inwall length to wing portion summit, b 1The inscribed circle radius of expression fibre section inwall.]
Polyester fiber with described shape of cross section can stand the impact that draw false twisting adds man-hour, after the draw false twisting processing, still has the performance that makes cloth and silk show abundant suction, rapid-drying properties.
And even above-mentioned polyester fiber carries out draw false twisting under common condition, draw false twisting adds also rare generation fracture of wire in man-hour (processing fracture of wire) and fluffing.And the flat degree of fiber cross section of gained draw false twisting processing silk to becoming different fiber cross section, forms the big fiber assembly in space between fiber along fiber axis in upwards appropriateness dispersion of fiber axis.The space can further improve the washing resistance of suction, rapid-curing cutback performance and this performance between big fiber like this.And the fiber assembly that the flat degree of fiber cross section is disperseed to appropriateness along fiber axis has the performance of bringing cloth and silk nature dry feeling concurrently.
Above-mentioned projection coefficient does not form the function of sufficient capillary interstice less than 0.3 wing portion on the fiber cross section after the draw false twisting processing, can't not demonstrate suction, rapid-drying properties.And so short and small wing portion is when applying the suction finishing agent to cloth and silk, and its fixation is little, makes the washing resistance of this finishing agent that the trend of reduction be arranged.The quality style of cloth and silk also becomes the paper as smooth (Off ラ Star ト).And the projection coefficient surpasses 0.7 wing portion, adds man-hour at draw false twisting, and machine tensions is concentrated in this wing portion easily, and partial destruction takes place in the fibre section, can't form sufficient capillary, and water absorbing properties is low.
Even the projection coefficient is the wing portion of 0.3-0.7, if having 1-2 this wing portion on the fiber cross section, then be closed in inboard fiber cross section part and only form maximum one, be difficult to embody capillarity, water absorbing properties reduces.In addition, the style of cloth and silk also becomes easily as smooth paper.And if surpass 8, then add man-hour at draw false twisting, machine tensions is concentrated in this wing portion easily, partial destruction takes place in the fibre section, can't form sufficient capillary, water absorbing properties reduces.
The degree of crystallinity of preferred above-mentioned polyester fibers having deformed section is below 30%, and boiling water shrinkage is more than 15%.Like this, the crystal region of this fiber does not increase, and it is upright and outspoken that fibre structure can not become, thereby under common draw false twisting condition, the fibre section flatness of draw false twisting processing silk is easy in upwards appropriateness dispersion of fiber axis.As a result, make suction, rapid-curing cutback performance and this performance washing resistance be further enhanced, and can show the natural dry feeling of cloth and silk.And make boiling water shrinkage is below 70%, can obtain stable fibre structure.
As the weaving method of above-mentioned polyester fibers having deformed section, can adopt known melt-spun method.For example, polyester is dry under common condition, melt extrude machine with screw extruder etc. and carry out fusion, disclosed spinnerets (Fig. 4) ejection from No. 3076372 Japan Patent for example, by always known method cooling, curing, batch then, dispose the spinneret orifice that forms wing portion on the spinnerets of wherein said Fig. 4, the spinneret orifice of this formations wing portion is individual in the circular spinneret orifice that forms core (Fig. 4 3) 3-8 on every side by arranged spaced, more preferably 4-6 small circular peristome (Fig. 4 5) and slit-like peristome (Fig. 4 4) are connected to form.Be the fiber that manufacturing has above-mentioned degree of crystallinity and boiling water shrinkage, preferred coiling speed be 2000-4000 rice/minute, more preferably 2500-3500 rice/minute.
At this moment, by changing the radius (b of Fig. 4 of the circular spinneret orifice that forms core 2), the central point of this circle spinneret orifice is to the length (a of Fig. 4 of the first end of the spinneret orifice that forms wing portion 2) etc., can set arbitrarily, the projection coefficient that makes the fibre section is 0.3-0.7.By changing spinning head temperature and/or cooling air quantity, the projection coefficient in controlling fiber cross section to a certain extent.In addition, as cooling air, preferably adopt the side direction type of cooling that is arranged at from the spinning tube air-supply of spinnerets below, the last end distance spinnerets below of spinning tube is 5-15cm, and length is 50-100cm.
The 4th purpose of the present invention is on the basis of first purpose, and a kind of polyester fibers having deformed section is provided, and can make the cloth and silk of the liquor style with bulk softness with this polyester fiber.This purpose realizes by following polyester fibers having deformed section.
Promptly, a kind of polyester fibers having deformed section, this polyester fiber contains the polyester polymers of polycondensation formation in the presence of above-mentioned special catalyst as main component, fiber cross section is by core and be radial outstanding a plurality of wing portion along the length direction of this core from core and constitute, and by the fiber that satisfies following (a)-(c) condition is simultaneously carried out the alkali decrement treatment, at least a portion that makes wing portion from core segment from.
1/20≤S B/S A≤1/3 (iv)
0.6≤L B/D A≤3.0 (v)
W B/D A≤1/4 (vi)
(S AThe sectional area of expression core; D ADiameter that should circle when the expression core section be circular or its circumscribed diameter during for circle; S B, L BAnd W BSectional area, maximum length and the Breadth Maximum of representing wing portion respectively.)
Fig. 5 represents the example and the S at this moment of above-mentioned fiber cross section A, D A, S B, L BAnd W B
Here, as 1/20>S B/ S AOr 1/3<S B/ S AThe time, promptly exist its sectional area less than core section long-pending 1/20 or during greater than 1/3 wing portion, the bulkiness of strand descends.
0.6>L B/ D AThe time, when promptly having its maximum length less than 0.6 times of core diameters wing portion, the bulkiness of strand descends, and 3.0<L B/ D AThe time, when promptly existing its maximum length to surpass 3.0 times of core diameters wing portion, wing portion can curl, and the quality quality becomes thick and stiff.
And then, work as W B/ D A>1/4 o'clock, when promptly having its Breadth Maximum greater than 1/4 wing portion of core diameters, be difficult to by the alkali decrement treatment make the wing part from.
The Breadth Maximum of above-mentioned wing portion is more little, then easy more by the alkali decrement treatment make the wing part from, but if this width becomes too small, then wing portion will bend, so preferred W B/ D AMinimum of a value terminate in about 1/8.
If the size to strand core and wing portion is specifically described, then the DENIER of wing portion is preferably below the 0.9dtex, more preferably below the 0.7dtex.The DENIER of wing portion is excessive, then can not obtain superfine feel by division wing portion, if increase wing portion area, then can make the drapability variation because of division.The fiber number of preferred core is below the above 5dtex of 1dtex.The fiber number of core surpasses 5dtex, even then wing portion and core division can not obtain sufficient soft feeling, the liquor style of fabric has the trend of hardening.And fiber number is less than 1dtex, even the multiple leaf-shaped section of sharp shape is then arranged, filling effect also can improve mutually, is difficult to effectively obtain big space.
Containing in the polyester fiber before the preferred bases decrement treatment with respect to this total weight of fiber is that (χ of parameter of consistency vii) is the compound of 0.1-2.0 for the following formula of 0.5-5.0% weight.Help separating of wing portion and core like this, obtain bigger bulkiness and the style that improves the quality.
χ=(Va/RT)(δa-δb) 2 (vii)
In the following formula, Va represents the molal volume (cm of polyester 3/ mol), R represents gas constant (J/molK), and T represents absolute temperature (K), and δ a and δ b represent the solubility parameter (J of polyester and above-claimed cpd respectively 1/2/ cm 3/2).
Here, χ was less than 0.1 o'clock, and polyester and above-claimed cpd are compatible, be difficult to by alkali decrement treatment generation wing part from.And χ surpasses at 2.0 o'clock, and polyester and above-claimed cpd are separated fully, and be polymer-thickened, and spinnability has a declining tendency.
The combined amount of above-claimed cpd in polyester is difficult to obtain the effect that improves bulkiness during less than 0.5% weight, and content is when surpassing 5.0% weight, and aggegation easily takes place above-claimed cpd, is difficult to obtain required effect equally.
The object lesson of above-claimed cpd has polyethylene, polypropylene, polyisobutene, polystyrene, polytetrafluoroethylene (PTFE), polychlorostyrene tetrem alkene, polychlorotrifluoroethylene, polyvinyl proprionate, polyacrylic acid seven fluorine butyl esters, polybutadiene, polyisoprene, polychlorobutadiene, polyethylene glycol, polytetramethylene glycol, poly-triethylene glycol, PMA, the polyacrylic acid propyl ester, butyl polyacrylate, polyisobutyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polybenzyl methacrylate, the polymethylacrylic acid ethoxy ethyl ester, polyformaldehyde, polyethylene sulfide, polymer and siloxanes or their modifiers etc. such as polystyrene sulfide.Above-claimed cpd can be used in combination.
If the mean molecule quantity of above-claimed cpd is too small, when then being detained in extruder or spinning head, thermal decomposition will take place, and if molecular weight is excessive, then with the melting mixing decline of polyester, so preferred mean molecule quantity is 3000-25000.
In addition, when being mixed into the above-claimed cpd interpolation in the polyester, can adopt always known method arbitrarily, for example with process for granulating after polyester and the above-claimed cpd melt kneading; In the melt-spun operation, in molten polyester, spray the method for mixing above-claimed cpd; The method of mixing by static mixer etc.
Can obtain the preceding polyester fiber of alkali decrement treatment by for example following method.
Promptly, the polyester that will spray by the spinneret orifice fusion that forms core, with by the slit-like spinneret orifice fusion that is a plurality of formation wing portion of radial arranged spaced around this spinneret orifice ejection with above-mentioned the same polyester, under molten condition, connect, with its cooling curing.
Specifically, make above-mentioned polyester via as shown in Figure 6A spinnerets fusion ejection exactly, to be connected under molten condition with the material that sprays from spinneret orifice 6 from the material of spinneret orifice 5 ejections, cooling curing then, wherein said spinnerets have the circular spinneret orifice 5 that forms core and are the slit-like spinneret orifice 6 that a plurality of (in Fig. 6 A be 4) of radial arranged spaced around this circle spinneret orifice 5 forms wing portion.
Can implement stretching or heat treatment etc. to spun strand as required.
Here, wing portion number is 1 or 7 when above, and the space in the strand that forms by the alkali decrement treatment diminishes, and is difficult to make it to have sufficient bulkiness.1 preferred number that forms the slit-like spinneret orifice of the formation wing portion that disposes around the spinneret orifice of core is 3-6, more preferably 4.The sectional area of each wing portion, maximum length and Breadth Maximum are not necessarily leaveed no choice but identical, can be different separately.And preferably each wing portion is the center with the core, and it is radial outstanding that isotropism is, but also be not limited thereto.
Among the present invention, circular spinneret orifice 5 that forms core and the size that forms the slit-like spinneret orifice 6 of wing portion are not particularly limited, but for sectional area, maximum length and the Breadth Maximum of the sectional area that makes core and diameter, each wing portion in the scope of above-mentioned 3 formula (a) and (b), (c) regulation, preferably with D ' AThe diameter of the circular spinneret orifice 5 of expression formation core (when the cross sectional shape of spinneret orifice 5 is not circle, D ' AThe circumscribed diameter of expression spinneret orifice 5.), with L ' BAnd W ' BRespectively expression form the maximum length of slit-like spinneret orifice 6 of wing portion and Breadth Maximum, with L ' ABDuring the shortest interval between the spinneret orifice 5 and 6 on the expression spray silk face, D ' A, L ' B, W ' BAnd L ' ABSatisfy following key element simultaneously (viii)-(x).
1≤L’ B/D’ A≤4 (viii)
1/7≤W’ B/D’ A≤1/2 (ix)
0.01mm≤L’ AB≤0.2mm (x)
D ' A, L ' B, W ' BAnd L ' ABIn the time of outside above-mentioned scope, the situation of spinning state variation, spinnerets quick abrasion can appear.
If differing, the slit-like spinneret orifice of formation wing portion establishes a capital the same rectangle, can be shown in Fig. 6 B, and a part has circular-arc dilation thereon, and perhaps its width recurs variation.
On the other hand, if replace above-mentioned two kinds of spinneret orifices 5,6 (or 6 ') to shoot out polyester with single spinneret orifice, make strand with above-mentioned core and wing portion, then core and wing portion are as a whole, and the orientation of core and wing portion is roughly the same, have be difficult to by alkali decrement treatment described later make wing part from tendency.
When the spinning that as above illustrates, the polymer that sprays from the slit-like spinneret orifice that forms wing portion is subjected to bigger drawing-off than the polymer that sprays from the spinneret orifice that forms core, so the orientation of the orientation ratio core of wing portion is higher.Therefore, in above-mentioned strand, particularly the molecule interlacing at the joint face place of core and wing portion is few, the interface binding power of joint face is little, by carrying out the alkali decrement treatment, wing portion separates from the part core with advantage, and because of the misorientation of core and wing portion shrinks poorly, can obtain to have the strand of required bulkiness and soft liquor style.
Among the present invention, the gained strand is carried out the alkali decrement treatment, at least a portion of wing portion from core segment from, freely give prominence to fibre end (fluffing) because of cut-out forms be effective but this separation method is for suppressing wing portion or core as far as possible.By prior art as can be known, the physical means that employing utilizes the very big energy of generation of fluid tip processing of high pressure compressed air-flow etc. to move divides strand, to form in a large number and freely give prominence to fibre end, and wing portion ftractures into the fibril shape, thereby the outward appearance that will present short fibre yarn when making fabric, the neat and well spaced property of fabric is impaired.
Above-mentioned alkali decrement treatment can be implemented under any state of silk, yarn or fabric.But the state that is preferably in fabric is implemented down.The alkali treatment condition can directly adopt the alkali treatment condition of common polyester fiber.Specifically, use the aqueous solution of NaOH, potassium hydroxide, sodium carbonate, potash etc., suitably setting concentration is the 10-100g/ liter, and design temperature is 40-180 ℃, sets the processing time and is 2 minutes to 2 hours and get final product.
Preferably the separation rate S of the wing portion that obtains by the alkali decrement treatment is more than 30%, and be positioned at the multifilament skin section silk the separation rate S of wing portion than be positioned at the multifilament central part thread the separation rate S of wing portion big.Here, the separation rate S of wing portion is the value with the following formula definition.
S (%)=(the wing portion number of separation/wing portion sum) * 100
The silk that is arranged in the multifilament skin section is meant sum at above-mentioned leafy shape silk, begins silk in 30% scope recently apart from the imaginary circumcircle of multifilament on the multifilament cross section.The silk that is positioned at the multifilament centre is meant with above-mentioned the same, begins the silk in 30% scope recently apart from imaginary circumscribed center.
By such alkali decrement, can obtain as shown in Figure 7 wing portion from core segment from single fiber.Fig. 7 is the part enlarged drawing of seeing from the side of an above-mentioned polyester fibers having deformed section example, 4 expression single fibers, 1 expression core, the major part that 2,3 expressions are radial outstanding wing portion from core be in from core segment from state.
In the illustrative polyester fibers having deformed section 4 of Fig. 7, be connected with core 1, be radial outstanding wing portion 2,3 from core 1 and separate from core 1, become independently silk by the alkali decrement treatment along the length direction of core 1.
Shown in the wing portion 2 of Fig. 7, preferred above-mentioned wing portion separates from core 1 in the whole length of single fiber continuously, this wing portion is resembled independently work the silk.But, not necessarily to all wing portions all in the length range of silk, separate, also can there be the part that is connected with core as wing portion 3.
Wing portion is separated from core 1, can make between the core contiguous in the fabric for example and have sufficient space, that the bulkiness of fabric becomes is relatively good (silk shown in Figure 5 has 4 wing portions with respect to 1 core, but among Fig. 7 with respect to 1 core only illustration 2 wing portions 2,3).
Preferably with between above-mentioned polyester fibers having deformed section and this fiber or with other mixed with fibers, interlacing, form mixed filament, make fabric then, carry out the alkali decrement treatment afterwards again.Can adopt doubling, mix always known any methods such as sth. made by twisting, air interlacing,, make mixed filament mixed with fibers, interlacing.
The 5th purpose of the present invention is on the basis of first purpose, and a kind of polyester fibers having deformed section is provided, can make with this polyester fiber to have rough harsh feeling, and loftiness, flexibility, light weight sense excellence, and do not have the cloth and silk of the silk style of uneven dyeing.This purpose realizes by following polyester fibers having deformed section.
Promptly, a kind of polyester fibers having deformed section, this polyester fiber contains the polyester polymers of polycondensation formation in the presence of above-mentioned special catalyst as main component, the fiber cross section shape is made of gable and the protuberance that extends out from this leg-of-mutton summit, satisfy following formula simultaneously (viii) and (ix), and have the hollow space of 3-15% in this gable.
0.7≤L1/L2≤3.0 (viii)
3.0≤h2/h1≤10.0 (ix)
(L1 represents the distance from the tie point of gable and protuberance to the protuberance other end, L2 represents that tie point from gable and protuberance is to the distance the gable opposite side relative with this tie point, h1 represents the width of protuberance, h2 represent with respect to the gable of the tie point of gable and protuberance to edge lengths.)
Here, when the position that extends out of protuberance is not the summit of gable, but for example when gable central authorities on one side extend out, spinnability will descend, perhaps protuberance is when a plurality of summits extend out, not only spinnability can descend, and the liquor style of gained cloth and silk also becomes and do not resemble wild silkworm, thereby not preferred.When the shape of protuberance is not a flat, but for example during the such shape of circular cross section, the harsh feeling of gained cloth and silk will reduce, thereby not preferred.Here said flat need be in gamut thickness homogeneous all, wherein a part is thicker than other parts.In a word, as long as the ratio (L1/h1) of the length (L1) of following protuberance and width (h1) is more than 2, particularly get final product more than 5.This ratio is less than 2 o'clock, the flat of can not saying so, and the gained cloth and silk lacks harsh feeling and flexibility, thereby not preferred.
The direction of extending from gable for protuberance, preferably this direction is in the formed angle of extended line on two limits of leg-of-mutton this drift angle of folder, particularly most preferably in the bisecting line direction of drift angle.
Below, the present invention will be described in more detail with reference to accompanying drawing.Fig. 8 is the ideograph that is used to illustrate the shape of cross section of above-mentioned polyester fibers having deformed section.Among Fig. 8, the mid point O between the periphery of gable (A) and the periphery of flat protuberance intersect 2 is that the tie point of gable and flat protuberance (for for simplicity, is represented with justifying in vain among the figure.)。This tie point is the length L 1 of protuberance to the distance of the protuberance other end, and this tie point is L2 to the distance of the opposite side of gable (A).When this opposite side expands laterally, when caving in to the inside, connects two summits beyond the tie point on the triangle with straight line, be parallel to this straight line and do and the tangent straight line of this opposite side, with to the distance of this tangent line as L2.
In addition, with the flat protuberance perpendicular to the width h1 of the Breadth Maximum on the direction of protuberance (B) bearing of trend as protuberance (B), with perpendicular to above-mentioned opposite side and and tangent two straight lines of this gable (A) between the interval as the length h2 of opposite side.
(viii) stipulated the relation between the length of the size of gable (A) and flat protuberance (B), very important to harsh feeling, flexibility and the loftiness of comprehensive realization gained cloth and silk, preferred especially L1/L2 is in the 1.5-2.5 scope for above-mentioned formula.This value was difficult to comprehensively realize the harsh feeling and the flexibility of gained cloth and silk less than 0.7 o'clock, and surpassed at 3.0 o'clock, was difficult to spinning stably, and the gained cloth and silk lacks loftiness simultaneously, thereby not preferred.
Above-mentioned formula (ix) has been stipulated the relation between the width of the size of gable (A) and flat protuberance (B), and very important to the loftiness that realizes the gained cloth and silk, preferred especially h2/h1 is in the 4.0-7.0 scope.This was worth less than 3.0 o'clock, the loftiness deficiency of gained cloth and silk, and surpass at 10.0 o'clock, the spray silk stability decreases during spinning is difficult to spinning stably, thereby not preferred.
For making cloth and silk have light weight sense, loftiness etc., must make gable (A) have hollow rate is hollow space more than 3%.But if hollow rate is excessive, then stablizing spinnability will descend, so will be made as below 15% with respect to the hollow rate of this gable (A).Preferred this hollow rate is proper in the 3-10% scope.
Among the present invention, it is metal organic sulfonate shown in the following general formula (V) of 0.5-2.5% weight that preferred above-mentioned polyester contains with respect to weight polyester, because can pass through the alkali decrement treatment like this, at the micropore of the surface of polyester fibers having deformed section formation along the fiber axially-aligned, improve dry feeling and harsh feeling, obtain the cloth and silk that the utmost point resembles tussah silk.
R 9SO 3M (V)
(R 9The expression carbon number is the alkyl of 3-30 or aryl or the alkylaryl that carbon number is 7-40, and M represents alkali metal or alkaline-earth metal.)
In the following formula, R 9When expression alkyl or alkylaryl, this alkyl can be the straight chain shape, also can have the side chain of branch.From considering that with the compatibility of polyester preferred especially R is the alkyl sulfonic acid slaine of alkyl.M is alkaline-earth metal such as alkali metal such as sodium, potassium, lithium or calcium, magnesium, wherein preferred sodium, potassium.Such metal organic sulfonate concrete example is if any stearyl sodium sulfonate, sodium octyl, lauryl sulfonic acid sodium salt etc.
For example can adopt following method to make above-mentioned polyester fibers having deformed section.
Fig. 9 is the ideograph of a kind of spinneret orifice shape example of the expression spinnerets that is used to spin above-mentioned polyester fibers having deformed section.
That is, make polyester under 280-300 ℃ temperature, from having the spinnerets fusion ejection of above-mentioned spinneret orifice shape, cooling curing oils for spun strand, makes its interlacing by the interlacing device as required, via a pair of carry-over pinch rolls that are set at room temperature, undrawn yarn is coiled into winder then.Then, with the gained undrawn yarn with 600-1400 rice/minute draw speed, via being heated to 80-110 ℃ preheat roll and being set at 170-240 ℃ contactless heater, stretch with 1.5-3.0 stretching ratio doubly, can also make its interlacing as required.
Consider that from stability of spinning process preferred melt-spun temperature is 275-300 ℃.Suitably set spinning hauling speed and stretching ratio, the intensity that makes polyester complex fiber is 2.0-5.0cN/dtex, and percentage elongation is 30-50%.
The single fiber fiber number of preferred above-mentioned polyester fibers having deformed section is 1.5-5.0dtex, and the total fiber number of strand is 50-170dtex, and boiling water shrinkage is suitable in the 5.0-12.0% scope in addition.
When weaving cloth and silk, can suitably twist as required, be woven into required tissue with above-mentioned polyester fibers having deformed section.Can be as required, the gained cloth and silk is implemented the alkali decrement treatment, obtain to possess the fabric of excellent harsh feeling that existing fabric do not have and loftiness, flexibility, light weight sense.
In the above-mentioned purpose, because purpose is light weight, harsh feeling, so tissue preferably not woven, that be knitted into complexity preferably is woven into plain weave or its alternative construction, simple twill-weave or its alternative construction, satin weave etc.It is 100% that profiled fibre of the present invention shared ratio in cloth and silk is not necessarily leaveed no choice but, but for obtaining excellent harsh feeling and loftiness, flexibility, light weight sense, preferably its ratio is The more the better.
Embodiment
Below, by embodiment the present invention is carried out more specific description.But the present invention is not limited to these embodiment.By the projects among the following method mensuration embodiment.
(1) inherent viscosity
Use o-chlorphenol as solvent, 35 ℃ of mensuration.
(2) flexibility
Carry out sensory evaluation by sense of touch, following being judged to be:
3: softness is fabulous;
2: good;
1: coarse hard sense is arranged, bad.
(3) barrier property
Measure L value, the L value during the L value during Δ L=use blank-use blackboard, numerical value is more little, and barrier property is excellent more.
(4) gas permeability
With JIS L-1096-79-6.27 gas permeability A method is benchmark, uses Fu Leize type Air permenbility tester to measure.
(5) water imbibition
Measure by JIS1096 " Byreck method ".
(6) mar proof
With マ-チ Application デ-Le abrasiometer friction 3000 times, will not see that being judged as of cloth and silk wearing and tearing is good, being judged as of can confirming to wear and tear is bad.
(7) titanium elements content, phosphorus element content
With granular polyester test portion heating and melting on aluminium sheet, on the compression stamping machine, it is pressed into the test molded item with tabular surface then, fluorescent X-ray determinator 3270 types that use electrical industry of science Co., Ltd. to make are measured titanium elements content and phosphorus element content.
(8) (L *-b *) value
(ゲ-ジ) circular knitting machine is made the long braiding grey tube cloth of 30cm, with the Macbeth woven color determinator of company (COLOR-EYE), measures L with 12 needle gages with polyester fiber *Value, b *Value, its difference is (L *-b *) value.
(9) play approximate number (individual/10 6Rice)
The bobbin (or spindle) of 250 polyester fibers is contained on the warping machines with fluffing checkout gear,, carries out warping traction in 42 hours with 400 meters/minute speed.When warping machines was shut down, visual examination had or not fluffing, and the fluffing sum that confirms is converted into per 10 6Rice fiber strand silk length play approximate number, with this as an approximate number.
Embodiment 1
The preparation of titanium compound:
Preparation has the 2L three-neck flask that can mix the device that stirs content, to 919g ethylene glycol and the 10g acetate of wherein packing into, mixes and stirs, and slowly adds 71g four titanium butoxide in this mixture, makes the ethylene glycol solution (transparent) of titanium compound.Hereinafter this solution note is made " TB solution ".The titanium atom concentration of this solution is 1.02%.
The preparation of phosphorus compound:
Preparation has the 2L three-neck flask that can heat, mix the device that stirs content, to the 656g ethylene glycol of wherein packing into, is heated to 100 ℃ while stir.When reaching said temperature, add 34.5g phosphoric acid one lauryl, heating mixes stirs, and transparent solution is made in dissolving.Below, this solution note is made " P1 solution ".
Preparation of catalysts:
Then, in heating is controlled at 100 ℃ above-mentioned P1 solution (about 690g), slowly add the preprepared TB solution of 310g while stirring, after all adding, under 100 ℃ temperature, stir and kept 1 hour, the reaction of titanium compound and phosphorus compound is finished.Adjust this moment TB solution with the combined amount ratio of P1 solution, making phosphorus atoms is 2.0 with respect to the molar ratio of titanium atom.The product that this reaction generates is insoluble to ethylene glycol, so reactant liquor presents the gonorrhoea state, product exists wherein with fine precipitation form.Below, this solution note is made " TP1-2.0 catalyst ".
In order to analyze the gained reaction precipitation, the filter of a part of reaction solution with hole 5 μ filtered, collect the above-mentioned precipitated product of solid form, then washing, drying.The gained precipitated product is carried out the concentration of element analysis by the XMA analytic approach, and titanium is 12.0% as a result, and phosphorus is 16.4%, and phosphorus atoms is 2.1 with respect to the molar ratio of titanium atom.Further carry out the solid NMR analysis, obtain following result.By C-13CP/MAS (frequency 75.5Hz) determination method, affirmation has disappeared from chemical shift 14ppm, 20ppm, the 36ppm peak of the butoxy of four titanium butoxide, by P-31DD/MAS (frequency 121.5Hz) determination method, confirm non-existent new chemical shift peak 22ppm in phosphoric acid one lauryl originally.Hence one can see that, and the precipitation of gained is evident as the new compound of titanium compound and phosphorus compound reaction formation under this condition.
And then, at stirring, nitrogen atmosphere, keep under 255 ℃, the condition of normal pressure, the slurries that 179 parts of high purity terephthalic acids and 95 parts of ethylene glycol are mixed and made into are supplied with certain speed and are equipped with in advance in the reactor of 225 parts of oligomer, to react the water and the ethylene glycol that generate on one side distillates outside the system, carry out 4 hours esterification on one side, make reaction terminating then.The esterification yield of this moment is more than 98%, and the degree of polymerization of the oligomer of formation is about 5-7.
The oligomer that 225 parts of these esterifications are obtained moves in the polycondensation reaction groove, adds 3.34 parts of above-mentioned " TP1-2.0 catalyst " of making as polycondensation catalyst.Then, with the reaction temperature in the system from 255 ℃ of temperature-gradient methods to 280 ℃, and with reaction pressure from the atmospheric pressure split reduction to 60Pa, on one side the water and the ethylene glycol that generate in will react shift out outside the system, polycondensation reaction is carried out on one side.
By the load that stirrer paddle bore in the monitoring system, confirm the degree of carrying out of polycondensation reaction, when reaching the required degree of polymerization, cessation reaction.At this moment, in course of reaction, add titanium dioxide, make it reach 2.5% weight with respect to the polyester gross weight as delustering agent.Afterwards, the reactant in the system is extruded the formation strip continuously from discharge gate, cooling, section, the granular section of making the about 3mm of particle diameter.The inherent viscosity of gained polyethylene terephthalate is 0.62.
With the spinning temperature of this polyethylene terephthalate particle at 290 ℃, from having the spinnerets spinning of 36 single fiber cross sectional shape spinneret orifices shown in Figure 1, oil agent, spinning speed with 3000 meters/minute draws, need not to batch, under the condition of 80 ℃ of preheat temperatures, 120 ℃ of heat setting temperatures, 1.67 stretching ratios, stretch, with 5000m/minute speed batch, obtain the multifilament that constitutes by flat cross section fiber of the present invention of single fiber degree 2.4dtex, total fiber number 86dtex.With the gained multifilament with 110/2.54cm knit density, the non-twist plain cloth that is woven into of graticule, by the conventional method processing of dyeing, estimate the gained cloth and silk then by above-mentioned the whole bag of tricks.The result is as shown in table 1.
Embodiment 2-3, comparative example 1
Change spinnerets, change spinneret orifice the shape of the single fiber cross sectional shape of (b)-(f) that can form Fig. 1 and circular cross section into, in addition, with embodiment 1 the same operation.The result is as shown in table 1.
Comparative example 2
The 1.3% concentration ethylene glycol solution that polycondensation catalyst is changed into antimony trioxide as, its addition is 4.83 parts, and 25% ethylene glycol solution that adds 0.121 part of trimethyl phosphate is as stabilizing agent, in addition, with embodiment 1 the same operation.The result is as shown in table 1.
Comparative example 3
The TB solution that only uses preparation among the embodiment 1 is as polycondensation catalyst, and its addition is 1.03 parts, in addition, and with embodiment 1 the same the operation.The result is as shown in table 1.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1 Comparative example 2 Comparative example 3
Cross sectional shape (a) (b) (c) Circular cross section (b) (b)
Flatness 3 3.7 4.5 - 3.7 3.7
Degree of profile 2 2 2 - 2 2
Flexibility 2 3 3 1 2 2
Stick together sense Do not have Do not have Do not have Do not have Do not have Do not have
Barrier property (Δ L) 13.5 12.0 11.0 15.0 12.0 11.0
Gas permeability 2.0 1.2 1.1 6.8 1.2 1.5
Water imbibition 50 55 50 20 55 50
Mar proof Well Well Well Well Well Bad
L *-b * 76 77 73 70 59 50
Fluffing (individual/10 6Rice) 0.04 0.05 0.05 0.05 2.70 0.80
Embodiment 4
In the mixture of 100 parts of dimethyl terephthalate (DMT)s and 70 parts of ethylene glycol, sneak into 0.009 part of tetra-n-butyl titanate (TBT), this mixture packed into can carry out in the rustless steel container of compressive reaction, be forced into 0.07MPa on one side, and be warming up to 240 ℃ from 140 ℃, carry out ester exchange reaction on one side, add 0.035 part of phosphonoacetic acid triethyl (TEPA) then, the terminated diester exchange reaction.
Afterwards, product is moved into aggregation container, be warming up to 290 ℃, under the high vacuum below the 26.67Pa, carry out polycondensation reaction, obtain polyethylene terephthalate.At this moment, in course of reaction, add titanium dioxide, make it reach 2.5% weight with respect to the polyester gross weight as delustering agent.The inherent viscosity of this polyethylene terephthalate is 0.62, the diethylene glycol (DEG) amount is 1.5%.Further the gained polyethylene terephthalate is granulated by conventional method.
With the spinning temperature of this polyethylene terephthalate particle at 290 ℃, from having the spinnerets spinning of 36 single fiber cross sectional shape spinneret orifices shown in Figure 1, oil agent, spinning speed with 3000 meters/minute draws, need not to batch, under the condition of 80 ℃ of preheat temperatures, 120 ℃ of heat setting temperatures, 1.67 stretching ratios, stretch, with 5000m/minute speed batch, obtain the multifilament that constitutes by flat cross section fiber of the present invention of single fiber degree 2.4dtex, total fiber number 86dtex.With the gained multifilament with 110/2.54cm knit density, the non-twist plain cloth that is woven into of graticule, by the conventional method processing of dyeing, estimate the gained cloth and silk then by above-mentioned the whole bag of tricks.The result is as shown in table 2.
Embodiment 5-6, comparative example 4
Change spinnerets, change spinneret orifice the shape of the single fiber cross sectional shape of (b), (c) and the circular cross section that can form Fig. 1 into, in addition, with embodiment 4 the same operations.The result is as shown in table 2.
Comparative example 5
In the mixture of 100 parts of dimethyl terephthalate (DMT)s and 70 parts of ethylene glycol, sneak into 0.064 weight portion calcium acetate monohydrate, this mixture packed into can carry out in the rustless steel container of compressive reaction, be forced into 0.07MPa on one side, and be warming up to 240 ℃ from 140 ℃, carry out ester exchange reaction on one side, add the phosphate aqueous solution of 0.044 weight portion, 56% weight concentration then, the terminated diester exchange reaction.
Afterwards, product is moved into aggregation container, add antimonous oxide, be warming up to 290 ℃, under the high vacuum below the 26.67Pa, carry out polycondensation reaction, obtain polyethylene terephthalate with amount shown in the table.In this course of reaction, with the embodiment 4 the same titanium dioxide that add.Further the gained polyethylene terephthalate is granulated by conventional method.
Except that the particle that uses above-mentioned polyethylene terephthalate, with embodiment 4 the same operations, the result is as shown in table 2.
Table 2
Embodiment 4 Embodiment 5 Embodiment 6 Comparative example 4 Comparative example 5
The Ti compound Kind TBT TBT TBT TBT -
Content (mmol%) 5 5 5 5 -
P-compound Kind TEPA TEPA TEPA TEPA -
Content (mmol%) 30 30 30 30 -
The Sb compound Kind - - - - Sb 2O 3
Content (mmol%) - - - - 31
P/Ti 6 6 6 6 -
P+Ti 35 35 35 35 -
Cross sectional shape (a) (b) (c) Circular cross-section (b)
Flatness 3 3.7 4.5 - 3.7
Degree of profile 2 2 2 - 2
Flexibility 2 3 3 1 2
Stick together sense Do not have Do not have Do not have Do not have Do not have
Barrier property (Δ L) 13.0 12 3 11.2 16.5 12.0
Gas permeability 2.1 1.4 1.2 7.0 1.2
Water imbibition 52 57 52 16 55
Mar proof Well Well Well Well Well
L *-b * 78 78 74 71 58
Fluffing (individual/10 6Rice) 0.03 0.04 0.02 0.04 3.10
Further the present invention is described by embodiment 7-12, comparative example 6-7.Projects in these embodiment, the comparative example are measured by following method.
(1) degree of crystallinity
Measure by wide-angle x-ray diffraction.The X-ray generator (ロ--Off レ Star Network ス RU-200) that adopts electric society of science to make is used through the Cu-K alpha ray of nickel filter filter monochromatizing and is measured scattering strength, and calculates degree of crystallinity by following formula.
Scattering strength/the total scatter intensity of degree of crystallinity=crystalline portion * 100 (%)
(2) boiling water shrinkage
Make the several 20 times reeled yarn of volume with the ryce gauging machine of 1.125 meters of frame girths, add the load of 0.022cN/dtex, hang on the scale plate, measure the long L of reeled yarn at initial stage 0Afterwards this reeled yarn was handled 30 minutes in 65 ℃ tepidarium, put coldly then, hang over once more on the scale plate, measure the length L after shrinking, calculate boiling water shrinkage with following formula.
(3) projection coefficient
Take the cross section microphotograph of polyester multifilament, measure from the inscribed circle center of single fiber cross section inwall to the length (a on wing portion summit 1) and the inscribed circle radius (b of fibre section inwall 1), calculate the projection coefficient with following formula.
Projection coefficient=(a 1-b 1)/a 1
(4) titanium elements content, phosphorus element content
With granular polyester test portion heating and melting on aluminium sheet, on the compression stamping machine, it is pressed into the test molded item with tabular surface then, fluorescent X-ray determinator 3270 types that use electrical industry of science Co., Ltd. to make are measured titanium elements content and phosphorus element content.
(5) spinnerets foreign matter height
After adopting method shown in each embodiment, condition to carry out melt-spun,, make the ejection polymer non-cohesive, take off spinnerets, by the spinnerets foreign matter height that adheres to, piles up around the measurement microscope spinneret orifice to spinnerets surface release agent spraying.Measure the spinnerets foreign matter height of all spinneret orifices, represent with their mean value.
(6) spinning wire broken rate (%)
Except the fracture of wire that human factor or machine factor cause, the spinning fracture of wire number of times of record spinning machine generation in service calculates spinning wire broken rate (%) with following formula.
Spinning wire broken rate (%)=[fracture of wire number of times/(running winder number * doff number)] * 100 here, the doff number is meant the number of times that batches that the undrawn yarn tube is reached scheduled volume (10kg).
(7) processing wire broken rate
The SDS-8 type draw false twisting processing machine that adopts ス グ ラ Star グ company to make carries out draw false twisting processing to 10kg volume polyester multifilament fiber tube, and 2 fracture of wire number of times in the 5kg volume polyester false twist yarn tube process made in record, with following formula calculating processing wire broken rate.
Processing wire broken rate=fracture of wire number of times/(running number of spindles * 2) * 100
(8) processing fluffing
With the DT-104 type fluffing counting device of Dongli Ltd.'s manufacturing, with 50 meters/minute speed, an approximate number of continuous 20 minutes mensuration false twist yarns generation.
(9) fabric quality style
With 600/meter draw false twisting processing silk is twisted, make the TWILL CLOTH cloth and silk that uses warp, parallel.Then, carry out concise, relaxation processes,, carry out 15% alkali decrement treatment,, after the air dry,, make fabric 170 ℃ of final typings of carrying out 45 seconds 130 ℃ of dyeing 30 minutes 180 ℃ of pre-setting dry heat treatment of carrying out 45 seconds at 100 ℃.The inspection personnel judges this fabric by sense of touch, by following benchmark ratings.
One-level: nature has dry and comfortable sense of touch.
Secondary: the sensation dry feeling has lacked some a little.
Three grades: smooth, the sense of touch as paper is arranged.
(10) water-absorbing fast-drying (wicking value)
Water absorption testing, 5.1.1 item absorption speed (method of dripping) according to JIS L1907 fibre, mensuration falls water droplet at the second number (wicking value) till the surface reflection does not take place on the test cloth surface of being made by the polyester false twist yarn, with this index as suction, rapid-drying properties.L 10Expression is by the wicking value (second) after the JIS L0844-A-2 method washing 10 times.
(11) (L *-b *) value
Polyester fiber is made the long braiding grey tube cloth of 30cm with 12 needle gage circular knitting machines, and the Hunter colour difference meter CR-200 that makes with ミ ノ Le Co., Ltd. measures L *Value, b *Value, its difference is (L *-b *) value.
Embodiment 7-9
The generation of preparation separately of titanium compound, phosphorus compound, catalyst and oligomer all with embodiment 1 the same carrying out.
225 parts of gained oligomer are moved into the polycondensation reaction groove, add 3.34 parts of above-mentioned " TP1-2.0 catalyst " of making as polycondensation catalyst.Then, with the reaction temperature in the system from 255 ℃ of temperature-gradient methods to 280 ℃, and with reaction pressure from the atmospheric pressure split reduction to 60Pa, on one side the water and the ethylene glycol that generate in will react shift out outside the system, polycondensation reaction is carried out on one side.
By the load that stirrer paddle bore in the monitoring system, confirm the degree of carrying out of polycondensation reaction, when reaching the required degree of polymerization, cessation reaction.Afterwards, the reactant in the system is extruded the formation strip continuously from discharge gate, cooling, the granular section about the about 3mm of particle diameter is made in section.The inherent viscosity of gained polyethylene terephthalate is 0.630.
Prepare the spinnerets that has worn 24 groups of spinneret orifice groups in advance, described spinneret orifice group based on the spinneret orifice of spinneret orifice shape same type shown in Figure 4, the spinneret orifice that has the formation wing portion of number shown in the table 1 respectively, the slot width of the spinneret orifice of this formation wing portion is 0.10mm, and this circle spinneret orifice central point is to the length (a of Fig. 4 of first end 2) be 0.88mm, form the radius (b of Fig. 4 of the circular spinneret orifice of core 2) be 0.15mm, this spinnerets is assembled in the spinning pack, install on the spinning head.The particle of above-mentioned polyethylene terephthalate 150 ℃ of dryings after 5 hours, by being equipped with the melt-spun equipment fusion of screw-type extruder, is imported in 295 ℃ the spinning head, from this spinnerets with ejection in jetting amount 40g/ minute.Then, from the side direction cooling type spinning tube that is arranged at the spinnerets below, end distance spinnerets sprays the long 60cm of face 10cm position on it, with 5Nm 3/ minute ratio, blow 25 ℃ cooling air to polymer flow, cool off, solidify, last spinning oil, speed with 3000 meters/minute is batched, and is had the pet fiber of degree of crystallinity shown in the table 3, boiling water shrinkage, wing portion number and projection coefficient respectively.Above-mentioned melt-spun operation was carried out 7 days continuously.
The gained pet fiber is loaded onto SDS-8 type draw texturing machine (3 friction disc false twist units that ス グ ラ Star グ company makes, 216 ingots), carry out draw false twisting processing for 600 meters/minute with stretching ratio 1.65,175 ℃ of heter temperatures, 3300/meter of twisting counts, draw false twisting speed, obtain the polyethylene terephthalate draw false twisting processing silk of fiber number 84dtex.Wicking value (L in embodiment 1-3, the comparative example 1 0And L 10), the result of fabric quality style, processing wire broken rate and processing fluffing is summarized in the table 3.
Comparative example 6
As polycondensation catalyst, its addition is 4.83 parts with 1.3% concentration ethylene glycol solution of antimony trioxide, and 25% ethylene glycol solution that adds 0.121 part of trimethyl phosphate is as stabilizing agent, in addition, and with embodiment 8 the same operations.The result is as shown in table 3.
Table 3
Embodiment 7 Embodiment 8 Embodiment 9 Comparative example 6
Polymerization catalyst The product of four titanium butoxide and phosphoric acid one lauryl The product of four titanium butoxide and phosphoric acid one lauryl The product of four titanium butoxide and phosphoric acid one lauryl Sb 2O 3
The titanium compound in the polymerization catalyst and the mixed proportion of phosphorus compound *1 2.0 2.0 2.0 -
Wing portion number 3 4 6 4
The projection coefficient 0.51 0.48 0.48 0.48
Degree of crystallinity (%) 21 22 22 20
Boiling water shrinkage (%) 59 56 55 57
Wicking value L 0(second) L 10(second) 0 10 0 3 0 7 0 11
Spinning is spinnerets foreign matter height (μ m) after 7 days 3.0 2.5 3.7 89
Spinning wire broken rate (%) in 7 days 0.3 0.5 1.0 5.4
Fluffing number (10 4Rice) 2 3 1 31
Draw false twisting processing wire broken rate (%) 3.2 3.4 4.2 25.4
(L *-b *) value 88 97 95 92
The classification of fabric quality style One-level One-level One-level One-level
*1: phosphorus atoms is with respect to the molar ratio of titanium atom.
Embodiment 10-11
In the mixture of 100 parts of dimethyl terephthalate (DMT)s and 70 parts of ethylene glycol, sneak into 0.009 part of tetra-n-butyl titanate (TBT), this mixture packed into can carry out in the rustless steel container of compressive reaction, be forced into 0.07MPa on one side, and be warming up to 240 ℃ from 140 ℃, carry out ester exchange reaction on one side, add 0.035 part of phosphonoacetic acid triethyl (TEPA) then, the terminated diester exchange reaction.
Afterwards, product is moved into aggregation container, be warming up to 290 ℃, under the high vacuum below the 26.67Pa, carry out polycondensation reaction, obtain inherent viscosity and be 0.630, the diethylene glycol (DEG) amount is 1.5% polyethylene terephthalate.By conventional method the gained polyethylene terephthalate is granulated.
Prepare the spinnerets that has worn 24 groups of spinneret orifice groups in advance, described spinneret orifice group based on the spinneret orifice of spinneret orifice shape same type shown in Figure 4, the spinneret orifice that has the formation wing portion of number shown in the table 1 respectively, the slot width of the spinneret orifice of this formation wing portion is 0.10mm, and this circle spinneret orifice central point is to the length (a of Fig. 4 of first end 2) be 0.88mm, form the radius (b of Fig. 4 of the circular spinneret orifice of core 2) be 0.15mm, this spinnerets is assembled in the spinning pack, install on the spinning head.The particle of above-mentioned polyethylene terephthalate 150 ℃ of dryings after 5 hours, by being equipped with the melt-spun equipment fusion of screw-type extruder, is imported in 295 ℃ the spinning head, from this spinnerets with ejection in jetting amount 40g/ minute.Then, from the side direction cooling type spinning tube that is arranged at the spinnerets below, end distance spinnerets sprays the long 60cm of face 10cm position on it, with 5Nm 3/ minute ratio, blow 25 ℃ cooling air to polymer flow, cool off, solidify, last spinning oil, speed with 3000 meters/minute is batched, and is had the pet fiber of degree of crystallinity shown in the table 4, boiling water shrinkage, wing portion number and projection coefficient respectively.Above-mentioned melt-spun operation was carried out 7 days continuously.
The gained pet fiber is loaded onto SDS-8 type draw texturing machine (3 friction disc false twist units that ス グ ラ Star グ company makes, 216 ingots), carry out draw false twisting processing for 600 meters/minute with stretching ratio 1.65,175 ℃ of heter temperatures, 3300/meter of twisting counts, draw false twisting speed, obtain the polyethylene terephthalate draw false twisting processing silk of fiber number 84dtex.Wicking value (L in embodiment 1-3, the comparative example 1 0And L 10), the result of fabric quality style, processing wire broken rate and processing fluffing is summarized in the table 4.
Comparative example 7
In the mixture of 100 parts of dimethyl terephthalate (DMT)s and 70 parts of ethylene glycol, sneak into 0.064 weight portion calcium acetate monohydrate, this mixture packed into can carry out in the rustless steel container of compressive reaction, be forced into 0.07MPa on one side, and be warming up to 240 ℃ from 140 ℃, carry out ester exchange reaction on one side, add the phosphate aqueous solution of 0.044 weight portion, 56% weight concentration then, the terminated diester exchange reaction.
Afterwards, product is moved into aggregation container, add antimonous oxide, be warming up to 290 ℃, under the high vacuum below the 26.67Pa, carry out polycondensation reaction, obtain inherent viscosity and be 0.630 polyethylene terephthalate with amount shown in the table.Further the gained polyethylene terephthalate is granulated by conventional method.
Except that the particle that uses above-mentioned polyethylene terephthalate, with embodiment 2 the same operations, the result is as shown in table 4.
Table 4
Embodiment 10 Embodiment 11 Embodiment 12 Comparative example 7
The Ti compound Kind TBT TBT TBT -
Content (mmol%) 5 5 5 -
The P compound Kind TEPA TEPA TEPA -
Content (mmol%) 30 30 30 -
The Sb compound Kind - - - Sb 2O 3
Content (mmol%) - - - 31
P/Ti 6 6 6 -
P+Ti(mmol%) 35 35 35 -
Wing portion number 3 4 6 4
The projection coefficient 0.51 0.48 0.48 0.48
Degree of crystallinity (%) 24 25 25 20
Boiling water shrinkage (%) 53 52 52 57
Wicking value L 0(second) L 10(second) 0 8 0 4 0 6 0 11
Spinning is spinnerets foreign matter height (μ m) after 7 days 5.4 3.6 8.1 89
Spinning wire broken rate (%) in 7 days 1.4 0.3 2.5 5.4
Fluffing number (10 4Rice) 1 1 0 31
Draw false twisting processing wire broken rate (%) 3.5 3.9 4.0 25.4
(L *-b *) value 90 96 91 88
The classification of fabric quality style One-level One-level One-level One-level
Further the present invention is described by embodiment 13-34, comparative example 8-11.Projects in these embodiment, the comparative example are measured by following method.
(1) Si cross sectional shape
Observation with the alkali decrement treatment of 3000 times of shootings before the photo in silk cross section, obtain the sectional area (S of core A) and diameter (D A), the sectional area (S of wing portion B), maximum length and Breadth Maximum (W B).
(2) spinning state
Carry out continuous 8 hours melt-spun, the situation that does not have fracture of wire fully is A, and the situation that single fiber fracture (fluffing) takes place is B, and the situation that fracture of wire takes place is C.
(3) the separation rate S of wing portion
Observation with the alkali decrement treatment of 1000 times of shootings after the photo in silk cross section, obtain the wing portion number of separation, calculate the separation rate S (%) of the wing portion of multifilament skin section and central part by following formula.
S (%)=(sum of the number of the wing portion of separation/wing portion) * 100
(4) liquor style of fabric
Bulkiness, soft feeling and drapability to fabric are carried out overall merit, carry out sense organ with the Pyatyi of A (fabulous)~E (bad) and judge.
(5) parameter of consistency χ
By the solubility in all kinds of solvents, obtain polyester and with this polyester microcosmic on solubility parameter δ a, the δ b of the compound that is separated, calculate by following formula.
χ=(V a/RT)(δa-δb) 2
In the following formula, V aMolal volume (the cm of expression polyester 3/ mol), R represents gas constant (J/molK), and T represents absolute temperature (K), and δ a and δ b represent the solubility parameter (J of polyester and compound respectively 1/2/ cm 3/2).
(6) spinnerets foreign matter height
After adopting method shown in each embodiment, condition to carry out melt-spun,, make the ejection polymer non-cohesive, take off spinnerets, by the height of the spinnerets foreign matter that adheres to, pile up around the measurement microscope spinneret orifice to spinnerets surface release agent spraying.Measure the spinnerets foreign matter height of all spinneret orifices, represent with their mean value.
Embodiment 13-21
919g ethylene glycol and 10g acetate are mixed stirring,, make the ethylene glycol solution (transparent) of titanium compound to wherein adding 71g four titanium butoxide.Subsequently, 656g ethylene glycol is crossed thermal agitation at 100 ℃, to wherein adding 34.5g phosphoric acid one lauryl, heating mixes stirs, and dissolving obtains clear solution.
Then, two solution are mixed at 100 ℃, after all adding, stir maintenance 1 hour, obtain the solution of gonorrhoea state at 100 ℃.Adjust the combined amount ratio of two solution this moment, making phosphorus atoms is 2.0 with respect to the molar ratio of titanium atom.Filter the gained white precipitate, washing, drying is made polymerization catalyst.
At stirring, nitrogen atmosphere, keep under 255 ℃, the condition of normal pressure, the slurries that 179 parts of high purity terephthalic acids and 95 parts of ethylene glycol are mixed and made into are supplied with certain speed and are equipped with in advance in the reactor of 225 parts of oligomer, to react the water and the ethylene glycol that generate on one side distillates outside the system, carry out 4 hours esterification on one side, make reaction terminating then.The esterification yield of this moment is more than 98%, and the degree of polymerization of the oligomer of formation is about 5-7.
The oligomer that 225 parts of these esterifications are obtained moves in the polycondensation reaction groove, add 3.34 parts of above-mentioned catalyst of making as polycondensation catalyst, and the compound that is separated on interpolation mixing and the polyester microcosmic, be decompressed to 1mmHg, carry out polymerization by following conventional method, be cut into granularly, obtain inherent viscosity and be 0.63 polyethylene terephthalate particle (hereinafter referred to as the polyethylene terephthalate section).It is as shown in table 5 to add the compound, the χ value of compound, the addition that mix.
This polyethylene terephthalate is cut into slices from the spinnerets with shape spinneret orifice shown in the 24 picture group 6B, in 275 ℃ of melt-out spinnings, the core of ejection is connected on one side with wing portion, side direction blowing spinning tube in cool off on one side, batch with 1000 meters/minute speed.
Subsequently, with the stretching-machine of the slit heater that possesses 150 ℃ of the hot-rolling of 90 ℃ of temperature and temperature,,, obtain the long filament of 60dtex/24 rhizoid to the heat treatment that stretches of the long filament after above-mentioned the batching with 2.55 times stretching ratio.
The gained long filament is made the braiding cylinder primary colors grey cloth (tube Knitting ground) of 20 needle gages, this braiding cylinder primary colors grey cloth is boiled processing 20 minutes in the sodium hydrate aqueous solution of concentration 40 grams per liters, carry out the alkali decrement treatment.
The spinning state of each embodiment, spinnerets foreign matter height, fabric quality style etc. are as shown in table 5.
Comparative example 8,9
Except that with antimony trioxide as the polymerization catalyst, equally with embodiment 15 and 18 respectively make polyethylene terephthalate section, spinning, with its respectively as a comparative example 8 and 9.The spinning state of each embodiment, spinnerets foreign matter height, fabric quality style etc. are as shown in table 5.
Table 5
Compound χ Addition (% weight) The number of wing portion S B/S A L B/D A W B/D A The spinning state Foreign matter height (μ m) Wing portion separation rate The liquor style of fabric
Skin section (%) Central part (%)
Embodiment 13 PEG 0.08 3.0 4 1/4 1.0 1/5 A 12 62 44 B
Embodiment 14 PEG 0.08 3.0 6 1/4 0.8 1/5 A 9 66 47 A
Embodiment 15 C 16H 31The PEG of base grafting 0.25 3.0 4 1/4 1.0 1/5 A 10 72 51 A
Embodiment 16 PE (30)/PMMA (70) copolymer 0.33 3.0 4 1/4 1.0 1/5 A 13 78 59 A
Embodiment 17 PE (90)/PMMA (10) copolymer 1.3 3.0 4 1/4 1.0 1/5 A 12 89 68 A
Embodiment 18 PE 2.2 3.0 4 1/4 1.0 1/5 A 14 70 52 B
Embodiment 19 PMMA 2.3 3.0 4 1/4 1.0 1/5 A 21 71 54 B
Embodiment 20 C 16H 31The PEG of base grafting 0.25 0.3 4 1/4 1.0 1/5 A 17 63 41 B
Embodiment 21 C 16H 31The PEG of base grafting 0.25 4.0 4 1/3 1.5 1/4 A 15 79 60 A
Comparative example 8 C 16H 31The PEG of base grafting 0.25 3.0 4 1/4 1.0 1/5 B 55 70 53 A
Comparative example 9 PE 2.2 3.0 4 1/4 1.0 1/5 C 61 71 53 B
Embodiment 22,23
Among the embodiment 22, gained long filament A and polyethylene terephthalate section among the embodiment 15 is sprayed from the spinnerets fusion with 18 groups of flat spinneret orifices (L/D=5), batch with 1500 meters/minute, stretch with 90 ℃ of preheat temperatures, 2.7 times of stretching ratios then, with 1.5kg/cm 2Compressed air is pressed, 1.5% overfeeding ratio, carries out interlacing by the interlacing nozzle with the long filament B that makes the 40dtex/18 rhizoid, makes mixed filament.
Use above-mentioned mixed filament, as warp, parallel, be made into the soft plain-weave silk fabric fabric with the yarn that has applied the S300T/M twist yarn.After the relaxation processes, carry out HEAT SETTING, carry out 20% alkali decrement treatment again.The liquor style of the separation rate of wing portion, fabric is as shown in table 6 in the shrinkage factor of long filament A, long filament B and mixing yield and the gained fabric.
Among the embodiment 23, to contain 0.05% weight and be 0.64 polyethylene terephthalate section as titanium dioxide, the inherent viscosity of delustering agent, from spinnerets with shape spinneret orifice shown in the 24 picture group 6B in 275 ℃ of melt-out spinnings, the core of ejection is connected on one side with wing portion, in side direction blowing spinning tube, cool off on one side, batch with 2500 meters/minute, after stretching with 90 ℃ of preheat temperatures, 1.8 times, by the heat treatment that relaxes of 150 ℃ of contactless heaters, 2% overfeeding ratio, obtain the long filament A of 60dtex/24 rhizoid.
In addition, with polyethylene terephthalate section melt-out spinning from spinnerets with 18 circular spinneret orifices, batch with 1500 meters/minute, after stretching with 90 ℃ of preheat temperatures, 3.0 times of stretching ratios then, obtain the long filament B of 40dtex/18 rhizoid.
With above-mentioned long filament A and long filament B, mix, weave by the method the same, and implement the alkali decrement treatment with embodiment 23.
Among the embodiment 22,23 in the shrinkage factor of gained long filament A and long filament B, blending ratio and the gained fabric liquor style of the separation rate of wing portion, fabric as shown in table 6.In addition, said here blending ratio is meant the blending ratio of long filament A with respect to whole mixed filaments (weight of the weight of long filament A+long filament B).
Table 6
Long filament A Long filament B The separation rate of wing portion The liquor style of fabric
Boiling water shrinkage (%) Dry-hot shrinkage (%) Blending ratio (%) Boiling water shrinkage (%) Skin section (%) Central part (%)
Embodiment 22 8 0.5 60 8 53 38 B
Embodiment 23 6 -5 54 6 52 37 A
Embodiment 24-32
In the mixture of 100 parts of dimethyl terephthalate (DMT)s and 70 parts of ethylene glycol, sneak into 0.009 part of tetra-n-butyl titanate (TBT), this mixture packed into can carry out in the rustless steel container of compressive reaction, be forced into 0.07MPa on one side, and be warming up to 240 ℃ from 140 ℃, carry out ester exchange reaction on one side, add 0.035 part of phosphonoacetic acid triethyl (TEPA) then, the terminated diester exchange reaction.The M of this moment P/ M Ti=3, M P+ M Ti=35.
Afterwards, product is moved into aggregation container, be warming up to 290 ℃, under the high vacuum below the 26.67Pa, carry out polycondensation reaction, obtain inherent viscosity and be 0.630, the diethylene glycol (DEG) amount is 1.5% polyethylene terephthalate.Further the gained polyethylene terephthalate is made section by conventional method.
This polyethylene terephthalate is cut into slices from the spinnerets with shape spinneret orifice shown in the 24 picture group 6B in 275 ℃ of melt-out spinnings, the core of ejection is connected on one side with wing portion, in side direction blowing spinning tube, cool off on one side, batch with 1000 meters/minute.
Subsequently, with the stretching-machine of the slit heater that possesses 150 ℃ of the hot-rolling of 90 ℃ of temperature and temperature,,, obtain the long filament of 60dtex/24 rhizoid to the heat treatment that stretches of the long filament after above-mentioned the batching with 2.55 times stretching ratio.
The gained long filament is made the braiding cylinder primary colors grey cloth (tube Knitting ground) of 20 needle gages, this braiding cylinder primary colors grey cloth is boiled processing 20 minutes in the sodium hydrate aqueous solution of concentration 40 grams per liters, carry out the alkali decrement treatment.
The spinning state of each embodiment, spinnerets foreign matter height, fabric quality style etc. are as shown in table 7.
Comparative example 10,11
In the mixture of 100 parts of dimethyl terephthalate (DMT)s and 70 parts of ethylene glycol, sneak into 0.064 weight portion calcium acetate monohydrate, this mixture packed into can carry out in the rustless steel container of compressive reaction, be forced into 0.07MPa on one side, and be warming up to 240 ℃ from 140 ℃, carry out ester exchange reaction on one side, add the phosphate aqueous solution of 0.044 weight portion, 56% weight concentration then, the terminated diester exchange reaction.
Afterwards, product is moved into aggregation container, add antimonous oxide, be warming up to 290 ℃, under the high vacuum below the 26.67Pa, carry out polycondensation reaction, obtain polyethylene terephthalate with amount shown in the table.Further the gained polyethylene terephthalate is made section by conventional method.
Except that using above-mentioned polyethylene terephthalate section, the same operation with embodiment 26 and 29 makes long filament, with its as a comparative example 10 and 11.The spinning state of each embodiment, spinnerets foreign matter height, fabric quality style etc. are as shown in table 7.
Table 7
Compound The Ti compound P-compound The Sb compound χ Addition (% weight) The number of wing portion S B/S A L B/D A W B/D A The spinning state Foreign matter height (μ m) Wing portion separation rate The fabric quality style
Kind Content mmol% Kind Content mmol% Kind Content mmol% Skin section (%) Central part (%)
Embodiment 24 PEG TBT 5 TEPA 30 - - 0.08 3.0 4 1/4 1.0 1/5 A 10 63 40 B
Embodiment 25 PEG TBT 5 TEPA 30 - - 0.08 3.0 6 1/4 0.8 1/5 A 8 67 46 A
Embodiment 26 C 16H 31The PEG of base grafting TBT 5 TEPA 30 - - 0.25 3.0 4 1/4 1.0 1/5 A 10 71 52 A
Embodiment 27 PE (30)/PM MA (70) copolymer TBT 5 TEPA 30 - - 0.33 3.0 4 1/4 1.0 1/5 A 12 77 61 A
Embodiment 28 PE (90)/PM MA (10) copolymer TBT 5 TEPA 30 - - 1.3 3.0 4 1/4 1.0 1/5 A 11 86 67 A
Embodiment 29 PE TBT 5 TEPA 30 - - 2.2 3.0 4 1/4 1.0 1/5 A 14 71 52 B
Embodiment 30 PMMA TBT 5 TEPA 30 - - 2.3 3.0 4 1/4 1.0 1/5 A 22 70 53 B
Embodiment 31 C 16H 31The PEG of base grafting TBT 5 TEPA 30 - - 0.25 0.3 4 1/4 1.0 1/5 A 16 66 43 B
Embodiment 32 C 16H 31The PEG of base grafting TBT 5 TEPA 30 - - 0.25 4.0 4 1/3 1.5 1/4 A 16 80 59 A
Comparative example 10 C 16H 31The PEG of base grafting - - - - Sb 2O 3 31 0.25 3.0 4 1/4 1.0 1/5 B 57 71 52 A
Comparative example 11 PE - - - - Sb 2O 3 31 2.2 3.0 4 1/4 1.0 1/5 C 65 73 52 B
Embodiment 33,34
Among the embodiment 33, gained long filament A and polyethylene terephthalate section among the embodiment 26 is sprayed from the spinnerets fusion with 18 groups of flat spinneret orifices (L/D=5), batch with 1500 meters/minute, stretch with 90 ℃ of preheat temperatures, 2.7 times of stretching ratios then, with 1.5kg/cm 2Compressed air is pressed, 1.5% overfeeding ratio, carries out interlacing by the interlacing nozzle with the long filament B that makes the 40dtex/18 rhizoid, makes mixed filament.
Use above-mentioned mixed filament, as warp, parallel, be made into the soft plain-weave silk fabric fabric with the yarn that has applied the S300T/M twist yarn.After the relaxation processes, carry out HEAT SETTING, carry out 20% alkali decrement treatment again.The liquor style of the separation rate of wing portion, fabric is as shown in table 8 in the shrinkage factor of long filament A, long filament B and mixing yield and the gained fabric.
Among the embodiment 34, to contain 0.05% weight and be 0.64 polyethylene terephthalate section as titanium dioxide, the inherent viscosity of delustering agent, from spinnerets with shape spinneret orifice shown in the 24 picture group 6B in 275 ℃ of melt-out spinnings, the core of ejection is connected on one side with wing portion, in side direction blowing spinning tube, cool off on one side, batch with 2500 meters/minute, after stretching with 90 ℃ of preheat temperatures, 1.8 times of stretching ratios, by the heat treatment that relaxes of 150 ℃ of contactless heaters, 2% overfeeding ratio, obtain the long filament A of 60dtex/24 rhizoid.
In addition, with polyethylene terephthalate section melt-out spinning from spinnerets with 18 circular spinneret orifices, batch with 1500 meters/minute, after stretching with 90 ℃ of preheat temperatures, 3.0 times of stretching ratios then, obtain the long filament B of 40dtex/18 rhizoid.
With above-mentioned long filament A and long filament B, mix, weave by the method the same, and implement the alkali decrement treatment with embodiment 33.
Among the embodiment 33,34 in the shrinkage factor of gained long filament A and long filament B, blending ratio and the gained fabric liquor style of the separation rate of wing portion, fabric as shown in table 8.
Table 8
Long filament A Long filament B The separation rate of wing portion The liquor style of fabric
Boiling water shrinkage (%) Dry-hot shrinkage (%) Blending ratio (%) Boiling water shrinkage (%) Skin section (%) Central part (%)
Embodiment 33 8.3 0.6 60 15.6 50 35 B
Embodiment 34 6.1 -4.0 54 16.1 56 39 A
Below, by embodiment 35-40, comparative example 12-13, the present invention is made more specific description.And by the projects among the following method mensuration embodiment.
(1) inherent viscosity
With o-chlorphenol as solvent, 35 ℃ of mensuration.
(2) polymer sprays thread attitude
In the spinning, observe the state that shoots out of the polymer that from spinnerets, sprays, carry out classification to shooing out state according to following benchmark.After composite spinning begins 1 hour, observe after 3 days and after 7 days.
One-level: the strand of ejection forms fixing substantially following streamline, stably moves.
Secondary: the strand that can see ejection has little bending, shakes, circles round etc.
Three grades: big bending takes place, shakes or circles round in the strand of ejection.Partial polymer contacts with spinnerets, and fracture of wire frequently takes place.
(3) hollow rate (%)
Measure the hollow bulb area (A) in each monofilament cross section and surround the area (B) in cross section with polyester fiber cross section microphotograph, calculate by following formula, with the mean value of the value on whole monofilament cross sections of being measured as hollow rate (%)
Hollow rate (%)=A/B * 100
(4) fiber number irregular (U%)
With woven USTER TESTER 4 types of Star エ Le ベ-ガ-ウ-ス -company, measure with 400 meters/minute translational speed.
(5) play approximate number (individual/10 6Rice)
The bobbin (or spindle) of 250 polyester fibers is contained on the warping machines with fluffing checkout gear,, carries out warping traction in 42 hours with 400 meters/minute speed.When warping machines was shut down, visual examination had or not fluffing, and the fluffing sum that confirms is converted into per 10 6Rice fiber strand silk length play approximate number, with this as an approximate number.
(6) uneven dyeing
Polyester fiber is made the long braiding grey tube cloth of 30cm with 12 needle gage circular knitting machines, and (テ ラ シ-Le Block Le-GFL), 100 ℃ of dyeing 40 minutes, the inspection personnel carried out classification according to following benchmark to level-dyeing property by visual with dyestuff.
One-level: even dyeing does not have uneven dyeing basically
Secondary: can see a small amount of streak or mottled specking
Three grades: can see a slice streak or mottled specking.
(7) intensity, percentage elongation
Measure according to JIS-L1013.
(8) liquor style
By 5 skilled persons three grades according to fabulous (excellent), good (very), bad (not all right), harsh feeling, loftiness, flexibility, light weight sense are graded, calculate liquor style by its mean value.
Embodiment 35
The generation of preparation separately of titanium compound, phosphorus compound, catalyst and oligomer all with embodiment 1 the same carrying out.
225 parts of oligomer that obtain by this esterification are moved into the polycondensation reaction groove, add 3.34 parts of above-mentioned " TP1-2.0 catalyst " of making as polycondensation catalyst.Then, with the reaction temperature in the system from 255 ℃ of temperature-gradient methods to 280 ℃, and with reaction pressure from the atmospheric pressure split reduction to 60Pa, on one side the water and the ethylene glycol that generate in will react shift out outside the system, polycondensation reaction is carried out on one side, the carbon number that adds 0.6% weight is that 8-20, average carbon atom number are 14 sodium alkyl sulfonate, reaction is extruded the formation strip with the reactant in the system from discharge gate after finishing continuously, cooling, the granular section about the about 3mm of particle diameter is made in section.The inherent viscosity of gained polyethylene terephthalate is 0.63.
The gained polyester granulate is passed through the conventional method drying, import then and equipped the spinning machine that melt extrudes machine (screw extruder), fusion, importing is equipped in the spinning pack in 290 ℃ the spinning head, melt-out spinning, the strand cooling curing with this ejection oils afterwards, carry out interlacing subsequently, batch with 1400 meters/minute speed again.The gained undrawn yarn is stretched under the condition of 90 ℃ of preheat roll temperature, 200 ℃ of HEAT SETTING heater (contactless) temperature, 2.3 times of stretching ratios, 800 meters/minute of draw speeds, carry out interlacing then, obtain 83dtex/24 rhizoid, hollow rate and be 15% polyester profiled cross-section fibers.In the spinning process, do not see the spinneret orifice of spinnerets and pile up foreign matter on every side, polymer sprays thread attitude stable for extended periods of time.
As warp and parallel, weave soft plain-weave silk fabric with the gained fiber, carry out concise, HEAT SETTING, alkali decrement processing (reduction rate 15%), dyeing, obtain the DYED FABRICS of cellulose fabric according to conventional method.The evaluation result of gained fiber and fabric is as shown in table 9.
Comparative example 12
With 1.3% concentration ethylene glycol solution of antimony trioxide as polycondensation catalyst, its addition is 4.83 parts, and in addition 25% ethylene glycol solution that adds 0.121 part of trimethyl phosphate is as stabilizing agent,, with embodiment 35 the same operations, obtain inherent viscosity and be 0.63 polyester.This polyester is carried out spinning, stretching by method, the condition the same with embodiment 1, obtain the polyester profiled cross-section fibers of 83dtex/24 rhizoid.In the spinning process, the foreign matter around the spinneret orifice of spinnerets increases in time, and the strand that can see ejection bends, shakes and circles round.And then with embodiment 1 the same operation, obtain DYED FABRICS.The result of gained fiber and fabric is as shown in table 9.
Table 9
Embodiment 35 Comparative example 12
Polycondensation catalyst TP1-2.0 Sb 2O 3
Polymer sprays thread attitude (rank) spinning spinning spinning after 7 days after 3 days after 1 hour 1 1 1 2 3 3
Fiber number irregular (U%) spinning is spinning spinning after 7 days after 3 days after 1 hour 0.6 0.5 0.5 0.8 1.2 1.8
Fluffing (individual/10 6Rice) spinning spinning spinning after 7 days after 3 days after 1 hour 0.06 0.07 0.07 1.1 2.5 3.2
Uneven dyeing (rank) spinning is spinning spinning after 7 days after 3 days after 1 hour 1 1 1 2 3 3
Liquor style Excellent Excellent
Intensity (cN/dtex) 2.2 2.1
Percentage elongation (%) 33 32
Embodiment 36-37, comparative example 13
Except that the shape of cross section of single fiber is respectively table 10 indicating value, carry out spinning, stretching according to method, the condition the same with embodiment 35, obtain polyester profiled cross-section fibers.With embodiment 35 the same operations, obtain DYED FABRICS again.The liquor style of gained fabric is as shown in table 10.
Comparative example 13
Except that the shape of cross section of single fiber is respectively the circular cross-section, carry out spinning, stretching according to method, the condition the same with embodiment 35, obtain polyester profiled cross-section fibers.With embodiment 35 the same operations, obtain DYED FABRICS again.The liquor style of gained fabric is as shown in table 10, but does not have harsh feeling fully.
Table 10
Embodiment 36 Embodiment 37 Comparative example 13
L1/L2 2.0 0.8 -
h2/h1 5.3 5.3 -
Liquor style Excellent Excellent Bad
Embodiment 38-40
Except that the hollow rate of fiber is respectively table 11 indicating value, carry out spinning, stretching according to method, the condition the same with embodiment 35, obtain polyester profiled cross-section fibers.With embodiment 35 the same operations, obtain DYED FABRICS again.The liquor style of gained fabric is as shown in table 11.
Table 11
Embodiment 38 Embodiment 39 Embodiment 40
Hollow rate (%) 3 8 13
Polymer sprays thread attitude (rank) spinning spinning spinning after 7 days after 3 days after 1 hour 1 1 1 1 1 1 1 1 1
Fiber number irregular (U%) spinning is spinning spinning after 7 days after 3 days after 1 hour 0.5 0.5 0.5 0.4 0.3 0.4 0.4 0.4 0.4
Fluffing (individual/10 6Rice) spinning spinning spinning after 7 days after 3 days after 1 hour 0.05 0.05 0.04 0.04 0.03 0.04 0.05 0.04 0.05
Uneven dyeing (rank) spinning is spinning spinning after 7 days after 3 days after 1 hour 1 1 1 1 1 1 1 1 1
Liquor style Excellent Excellent Excellent
Intensity (cN/dtex) 2.6 2.2 1.8
Percentage elongation (%) 39 33 24

Claims (16)

1. polyester fibers having deformed section, this fiber contains polyester polymers as main component, has odd-shaped cross section, it is characterized in that:
Above-mentioned polyester polymers is formed by aromatic dicarboxylic acid ester's polycondensation in the presence of catalyst,
Above-mentioned catalyst contains at least a composition that is selected from following mixture (1) and product (2),
Said mixture (1) is following compositions (A) and mixture (B):
(A) contain the titanium compound composition (A) of at least a being selected from (a) and compound (b),
(a) alkoxytitanium shown in the following general formula (I),
Figure C2003801101480002C1
In the formula (I), R 1, R 2, R 3And R 4A kind of alkyl and phenyl groups that be selected from of independent respectively expression with 1-20 carbon atom, m represents the integer of 1-4, m represents integer 2,3 or, 2,3 or 4 R at 4 o'clock 2And R 3Can be identical or different respectively;
(b) product of aromatic polycarboxylic acid or its acid anhydrides shown in the alkoxytitanium of above-mentioned general formula (I) and the following general formula (II),
Figure C2003801101480002C2
In the formula (II), n represents the integer of 2-4;
(B) contain the phosphorus compound composition (B) of compound shown at least a following general formula (III),
Figure C2003801101480002C3
In the formula (III), R 5, R 6And R 7Independent separately expression has the alkyl of 1-4 carbon atom, and X represents at least a being selected from-CH 2-Ji and-CH 2(Y) group of base (Y represents phenyl);
The mM value of contained titanium elements is M with the ratio (%) of above-mentioned aromatic dicarboxylic acid ester's mole numerical value in the above-mentioned titanium compound composition (A) Ti, the mM value of institute's phosphorus element-containing is M with the ratio (%) of above-mentioned aromatic dicarboxylic acid ester's mole numerical value in the phosphorus compound composition (B) P, with M TiAnd M PSatisfying following formula (i) and combined amount (ii) uses above-mentioned as mixture of catalysts (1):
1≤M P/M Ti≤15 (i)
10≤M P+M Ti≤100 (ii);
Above-mentioned product (2) is following compositions (C) and product (D):
(C) contain at least a titanium compound composition that is selected from the compound of alkoxytitanium (c) shown in the general formula (I),
(D) contain the phosphorus compound composition of phosphoric acid one Arrcostab shown at least a following general formula (IV),
In the following formula (IV), R 8Expression has the alkyl of 1-20 carbon atom or has the aryl of 6-20 carbon atom.
2. the polyester fibers having deformed section of claim 1, wherein in each composition of composition (C) of described composition (A) as mixture of catalysts (1) and above-mentioned product (2) as catalyst, alkoxytitanium (a) and alkoxytitanium (c) separately with the reaction mol ratio of the aromatic polycarboxylic acid of general formula (II) or its acid anhydrides 2: 1-2: in 5 scopes.
3. claim 1 or 2 polyester fibers having deformed section, wherein said as the reacting dose ratio of composition (D) in the product (2) of catalyst with composition (C), be converted into the ratio (P/Ti) of the molar weight of contained titanium atom in the molar weight of contained phosphorus atoms in the composition (D) and the composition (C), 1: 1-3: in 1 scope.
4. each polyester fibers having deformed section among the claim 1-3, wherein said aromatic dicarboxylic acid ester is being contained in the presence of the catalyst of titanium compound, the diester that the dialkyl by aromatic dicarboxylic acid and the ester exchange reaction of alkylene glycol ester make.
5. each polyester fibers having deformed section among the claim 1-4, wherein said aromatic dicarboxylic acid is selected from terephthalic acid (TPA), 1,2-naphthalenedicarboxylic acid, phthalic acid, M-phthalic acid, diphenyl dicarboxylic acid, biphenoxyl ethane dioctyl phthalate, described alkylene glycol is selected from ethylene glycol, butanediol, trimethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexylene glycol and 1, the 12-dodecanediol.
6. each polyester fibers having deformed section among the claim 1-5, its fiber cross section is a flat pattern, this flat pattern has the shape that 3-6 circular cross section is formed by connecting along length side.
7. the polyester fibers having deformed section of claim 6 is a benchmark with the fibre weight, and this fiber contains the inorganic particle of 0.2-10% weight.
8. claim 6 or 7 polyester fibers having deformed section, on the cross section of this fiber, the flatness of representing with major axis width A and ratio A/B perpendicular to the Breadth Maximum B of the minor axis of this major axis is 3-6.
9. each polyester fibers having deformed section among the claim 6-8, on the cross section of this fiber, the degree of profile of representing with the ratio B/C of the Breadth Maximum B of minor axis and minimum widith C (minimum widith of circular cross section connecting portion) is greater than 1 and less than 5.
10. each polyester fibers having deformed section among the claim 1-5, its fiber cross section is made of from the outstanding laterally wing portion of this core core and 3-8, and the projection coefficient that (iii) defines with following formula is 0.3-0.7,
Projection coefficient=(a 1-b 1)/a 1(iii)
In the following formula, a 1The inscribed circle center of expression fibre section inwall is to the length on wing portion summit, b 1The inscribed circle radius of expression fibre section inwall.
11. the polyester fibers having deformed section of claim 10, its degree of crystallinity are below 30%.
12. the polyester fibers having deformed section of claim 10 or 11, its boiling water shrinkage are 15-70%.
13. each polyester fibers having deformed section among the claim 1-5, this polyester fiber is by core and be radial outstanding a plurality of wing portion along the length direction of this core from core and constitute, and by to have satisfy simultaneously following formula (iv)-(fiber of cross sectional shape vi) carries out the alkali decrement treatment, the at least a portion that makes this wing portion from core segment from
1/20≤S B/S A≤1/3 (iv)
0.6≤L B/D A≤3.0 (v)
W B/D A≤1/4 (vi)
S AThe sectional area of expression core; D AWhen the expression core section be circular, the diameter that this is circular or when not being circle, its circumscribed diameter; S B, L BAnd W BSectional area, maximum length and the Breadth Maximum of representing wing portion respectively.
The following formula that it is 0.5-5.0% weight that 14. the polyester fibers having deformed section of claim 13, this polyester fiber contained with respect to this polyester fiber weight before the alkali decrement treatment (χ of parameter of consistency vii) is the compound of 0.1-2.0,
χ=(V a/RT)(δa-δb) 2 (vii)
V aMolal volume (the cm of expression polyester 3/ mol), R represents gas constant (J/molK), and T represents absolute temperature (K), and δ a and δ b represent the solubility parameter (J of polyester and compound respectively 1/2/ cm 3/2).
15. each polyester fibers having deformed section among the claim 1-5, this fiber cross section is made of gable and the protuberance that extends out from this leg-of-mutton summit, satisfy following relational expression simultaneously (viii) and (ix), and the hollow space that has 3-15% in this gable
0.7≤L1/L2≤3.0 (viii)
3.0≤h2/h1≤10.0 (ix)
L1 represents the distance from the tie point of gable and protuberance to the protuberance other end, L2 represents that tie point from gable and protuberance is to the distance the gable opposite side relative with this tie point, h1 represents the width of protuberance, h2 represent with respect to the gable of the tie point of gable and protuberance to edge lengths.
It is metal organic sulfonate shown in the following general formula (V) of 0.5-2.5% weight that 16. the polyester fibers having deformed section of claim 15, this fiber contain with respect to polyester fiber weight,
R 9SO 3M (V)
R 9The expression carbon number is the alkyl of 3-30 or aryl or the alkylaryl that carbon number is 7-40, and M represents alkali metal or alkaline-earth metal.
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