JP2895254B2 - Antistatic polyester fabric with excellent wear resistance - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic polyester fabric which has been subjected to an alkali weight reduction of 10% or more, and more particularly to an antistatic polyester fabric having excellent durability and antistatic properties. The present invention relates to an antistatic polyester fabric having excellent wear properties.

[0002]

BACKGROUND OF THE INVENTION Polyesters have been widely used in woven and knitted fabrics for clothing because of their many excellent properties. However, polyester fibers are natural fibers such as wool and silk,
Compared to cellulosic fibers such as rayon and acetate, acrylic fibers, etc., they are hydrophobic, so static electricity is more likely to be generated. Is restricted.

Heretofore, as a method for imparting antistatic properties to polyester fibers, polyoxyalkylene glycols, polyoxyalkylene glycol / polyamide block copolymers, and polyoxyalkylene glycol / polyester block copolymers substantially incompatible with polyester have been used. A method of blending a polymer or the like and further blending an organic or inorganic ionic compound to form a solid polyester fiber (for example, JP-B-44-31828, JP-B-60-11944, and JP-A-53-1984). 80497, JP-A-60-3
No. 9413), a method of forming a hollow polyester fiber by adding a small amount of an antistatic agent composed of a polyoxyalkylene glycol and a metal sulfonate (Japanese Patent Publication No. 60-56)
No. 802) is known. However, when the antistatic polyester fiber obtained by these methods is subjected to an alkali weight reduction treatment that is generally widely performed to improve the feeling of the polyester fiber, the weight loss is particularly reduced to an alkali weight loss rate of 20% by weight or more. In the case, the antistatic property is easily lost in the subsequent dyeing step at a temperature of 120 to 135 ° C., the color depth and sharpness when dyed are reduced, and the fibrils are formed by mechanical frictional force. However, there are drawbacks such as easy splitting, poor wear resistance, and insufficient mechanical properties such as tear strength. Further, there is a problem that a portion which is subjected to pressure before the weight reduction processing is fibrillated in the alkali weight reduction process and the portion looks white when dyed (hereinafter, may be referred to as a pressure reduction whitening phenomenon). found. This pressure loss whitening phenomenon is caused by a weight loss rate of 1
It is difficult to develop with an alkali weight loss of less than 0%, but the weight loss rate is 1%.
It becomes manifest when it becomes 0% or more. Weaving, knitting, scouring, presetting, etc., the parts that have received pressure history such as pin marks, scratches, attrition spots, etc. applied in the processing steps performed before the alkali weight loss, the weight loss rate applied thereafter is 10% This is a phenomenon that becomes whitish after passing through the above-mentioned alkali weight loss step and dyeing step. The phenomenon becomes more apparent as the alkali weight loss rate increases, and becomes a serious drawback of a woven or knitted product.

[0004] Furthermore, a method of localizing the antistatic property of a polyoxyalkylene glycol and a metal sulfonate to a high concentration in a core component of a core-sheath type composite fiber to enable a high alkali weight reduction treatment ( For example, Japanese Patent Publication No. 61-6883, Japanese Patent Application Laid-Open No. 55-122020, Japanese Patent Application
No. 28016). According to this method, an antistatic polyester fiber having relatively excellent antistatic properties can be obtained even when a high alkali weight reduction processing with a weight reduction rate of about 25% by weight or more is performed. However, if there is slight eccentricity or pinholes in the core-sheath structure, the core component is eluted by the alkali weight reduction treatment, and the hollow fabric becomes a hollow structure and the dyed fabric looks whitish. Since the problem of lowering occurs, the composite ratio of the core / sheath area is 4/1.
It has been proposed to reduce it to 1/1.
No. 7117). However, even if such a core-sheath structure is adopted, when an alkali weight reduction process with a weight reduction rate of 10% or more is performed, a pressure whitening phenomenon or a strong mechanical It is easy to divide into fibrils due to mechanical friction, and is not practical.

[0005]

As described in detail above, the present invention has excellent anti-static durability even after alkali reduction, and has a high pressure resistance during the passage of higher processing steps such as alkali reduction and dyeing. In fact, antistatic polyester fabrics that do not cause defects such as weight loss whitening and have excellent fibril resistance and abrasion resistance have not yet been proposed, and are strongly desired.

The present invention has been made in view of the above situation, and has been developed for a woven or knitted product which has been subjected to alkali weight reduction with a weight loss rate of 10% or more.
An object of the present invention is to provide an antistatic polyester fabric which has excellent antistatic properties and its washing durability, has no pressure loss whitening defect, and has excellent abrasion resistance.

[0007]

Means for Solving the Problems The present inventors have solved the above-mentioned problems and provided a core-sheath type conjugate fiber excellent in both antistatic properties, whitening resistance against pressure loss, whitening and abrasion resistance. We tried diligently to try. As a result, when the core-sheath type conjugate fiber is subjected to pressure or mechanical friction, the polyester matrix of the core component, in which the antistatic agent is vertically dispersed in a streak shape, and the polyester of the sheath component, in which the antistatic agent is not dispersed, It has been found that interfacial peeling occurs between the matrix and the degree of the interfacial peeling, which causes a pressure whitening phenomenon and fibrillation. In other words, the part subjected to pressure before the weight reduction processing has a large degree of separation at the interface between the core component and the sheath component,
It is presumed that fine cracks occur in the sheath component, but the alkali weight reduction treatment with a weight loss rate of 10% or more causes elution of the core component, and a part of the filament has a hollow structure so that the dyeing looks whitish. . In addition, it was found that at the part that was subjected to mechanical friction after the weight reduction processing, part of the interface between the core component and the sheath component was peeled off, and the sheath component was divided into fibrils. Based on these findings, as a result of intensive studies on the structure of the core-sheath composite fiber constituting the fabric excellent in both antistatic properties and whitening resistance and abrasion resistance, as a result of mixing in the core component, When the compounding amount of the antistatic agent and the core / sheath area composite structure are specified, surprisingly, the above-mentioned occurrence of the pressure-loss whitening phenomenon is remarkably suppressed, and the abrasion resistance is further improved. It was found that the purpose of the term can be achieved.

[0008] Such excellent antistatic endurance effect is manifested by localizing and dispersing the antistatic agent at a high concentration in polyester as the core component of the core-sheath composite fiber, resulting in pressure and mechanical stress. This is presumably because even when the friction was applied, interface separation between the core component and the sheath component and fibrillation of the sheath component became difficult to occur. The present invention has been completed as a result of repeated experiments based on such findings.

That is, the present invention provides a fabric comprising a core-sheath conjugate fiber in which both core and sheath components are made of aromatic polyester and a weight reduction rate of 10% or more has been subjected to alkali weight reduction. (A) a polyoxyalkylene glycol or a derivative thereof substantially non-reactive with an aromatic polyester and (b) an organic metal salt, wherein the aromatic polyester of the sheath component has an intrinsic viscosity of 0.55 or more, Has a thickness in the range of 2 to 10 μm, and has a core / sheath area composite ratio of 5/95 to 18/82, and the blending amount C of the polyoxyalkylene glycol or the derivative thereof present in the core component ₁ (% by weight), the amount of the organic metal salt C ₂
(% By weight), the outer peripheral length L ₀ of the composite fiber in a cross section perpendicular to the fiber axis, and the outer peripheral length L ₁ of the figure formed by the core component simultaneously satisfy the following expressions (1) to (3). This is an antistatic polyester fabric excellent in abrasion resistance.

(1) 2.0 ≦ C ₁ ≦ 7.0 (2) 0.2 ≦ C ₂ ≦ 3.0 (3) 2.2 ≦ (C ₁ + C ₂ ) × (L ₁ / L ₀ ) ^0.5 ≤
5.0 The aromatic polyester used as the base of the sheath component and the core component in the fiber constituting the fabric of the present invention is an aromatic polyester having an aromatic ring in a chain unit of a polymer, and is a bifunctional aromatic dicarboxylic acid. Alternatively, it is a polymer obtained by reacting an ester-forming derivative thereof with a diol or an ester-forming derivative thereof.

The bifunctional aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, orthophthalic acid,
1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,
4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,
4'-diphenylsulfonedicarboxylic acid, 4,4'-diphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 2,
5-anthracene dicarboxylic acid, 4,4′-p-terphenyl dicarboxylic acid, 2,5-pyridine dicarboxylic acid,
Examples include β-hydroxyethoxybenzoic acid and p-oxybenzoic acid, and terephthalic acid is particularly preferred.

These bifunctional aromatic carboxylic acids may be used in combination of two or more. If the amount is small, a difunctional aliphatic carboxylic acid such as adipic acid, azelaic acid, sebacic acid, dodecandioic acid, or a difunctional alicyclic carboxylic acid such as cyclohexanedicarboxylic acid is used together with these difunctional aromatic carboxylic acids. An acid, 5-sodium sulfoisophthalic acid and the like can be used alone or in combination of two or more.

The diol compounds include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol,
Aliphatic diols such as 2-methyl-1,3-propanediol, diethylene glycol and triethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol; aromatic diols such as bisphenol A and bisphenol S; Mixtures and the like are preferred. If the amount is small, a polyoxyalkylene glycol having both ends or one end unblocked can be copolymerized with these diol compounds.
Further, a polycarboxylic acid such as trimellitic acid and pyromellitic acid, and a polyol such as glycerin, trimethylolpropane and pentaerythritol can be used as long as the polyester is substantially linear.

Specific preferred aromatic polyesters include polyethylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4 '.
In addition to dicarboxylate and the like, copolymerized polyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / decane dicarboxylate and the like can be mentioned. Among them, polyethylene terephthalate and polybutylene terephthalate, which have well-balanced mechanical properties and moldability, are particularly preferred.

[0015] Such an aromatic polyester can be synthesized by any method. For example, when polyethylene terephthalate is described, terephthalic acid and ethylene glycol are directly reacted, a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid and ethylene oxide are reacted. The first step is a reaction to form a glycol ester of terephthalic acid and / or a low polymer thereof, and the second step is heating the product under reduced pressure to conduct a polycondensation reaction until a desired degree of polymerization is obtained.
It is easily produced by the reaction of the step.

The above-mentioned polyester may contain other thermoplastic polymers, for example, polyamides such as nylon-6, polyolefins such as polyethylene and polystyrene, to the extent that the physical properties of the polyester are not impaired. It is preferable that the same polyester is used for the sheath component and the core component, but different polyesters can be combined as long as they have affinity.

In the core-sheath conjugate fiber constituting the antistatic polyester fabric of the present invention, the aromatic polyester constituting the core component is added to a polyoxyalkylene glycol substantially non-reactive with the aromatic polyester. Or a derivative thereof is blended. Here, “substantially non-reactive” means that the copolymer does not substantially copolymerize with the polyester.

As such a polyoxyalkylene glycol or a derivative thereof, any of those conventionally proposed to be mixed with thermoplastic synthetic fibers to impart antistatic properties can be used. 5214
And Japanese Patent Publication No. 57-4724. Specifically, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like, and mainly oxyethylene units, such as oxypropylene units, oxycyclohexylene groups, phenylethyleneoxy groups, hexylethyleneoxy groups, and methyl-pentylethyleneoxy groups A block copolymer or a random copolymer containing an alkyl group-substituted oxyalkylene group such as a heptylethyleneoxy group and a methyl-hexylethyleneoxy group, or one end or both ends of a polyoxyalkylene-based polyether, Group, alkenyl group, cycloalkyl group, aryl group, alkylaryl group, hydroxyalkyl group, hydrocarbon group such as sodium sulfophenoxy group, or alkanoyl group, alkenoyl group, cycloalkyl Those blocked with an acyl group or a phosphate group such as an alkylcarbonyl group, an arylcarbonyl group or an alkylarylcarbonyl group, methanol, propanol, butanol, phenol, bisphenol A, propylene glycol, butylene glycol, neopentyl glycol, glycerin, triglyceride Examples thereof include, but are not limited to, polyoxyalkylene compounds bonded to the residue of a hydroxyl group-containing compound such as methylolpropane, triethanolamine, diglycerin, petaerythritol, and sorbitol. Such polyoxyalkylene glycols or derivatives thereof may be used alone or in combination of two or more.

If the average molecular weight of such a polyoxyalkylene glycol or a derivative thereof is too small, it is difficult to form a streaky dispersion form having a sufficient length in the polyester fiber, so that the antistatic property and its durability are insufficient. Therefore, the average molecular weight is 3000 or more, more preferably 500
It is preferably 0 or more. On the other hand, when the average molecular weight is 25
If it exceeds 000, the melt miscibility of the polyethylene glycol or a derivative thereof in the aromatic polyester is rapidly deteriorated, and the dispersion thereof becomes non-uniform. And the physical properties are poor, and the above-mentioned pressure whitening phenomenon occurs remarkably. Therefore, when a hydroxyl group is present at the terminal, the average molecular weight is preferably 25,000 or less, more preferably 22,000 or less, and both ends are hydroxyl groups. Otherwise, 1
It is preferably 6,000 or less, more preferably 14,000 or less.

The blending amount C ₁ of the polyoxyalkylene glycol or its derivative is 2 to 7% by weight based on the aromatic polyester constituting the core component of the core-sheath type conjugate fiber.
Range. If it is less than 2% by weight, sufficient antistatic properties cannot be obtained. On the other hand, when the amount exceeds 7% by weight, the antistatic property of the finally obtained polyester fiber no longer shows a remarkable improvement, and the mechanical properties, heat resistance and light resistance of the obtained fiber are rather impaired. In addition to
Alkali weight loss rate, visual infection color, pressure loss whitening, etc. all deteriorate.

In the present invention, an organic metal salt is mixed with the above-mentioned polyoxyalkylene glycol or its derivative in combination with the core component. Preferred organic metal salts include dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, nonylbenzenesulfonic acid,
Alkali metal salts of sulfonic acids formed from sulfonic acids such as dibutylnaphthalenesulfonic acid, hexadecylsulfonic acid, dodecylsulfonic acid and alkali metals such as sodium, potassium and lithium, and phosphate esters such as sodium distearylphosphate And alkali metal salts of other organic carboxylic acids. Furthermore, a metal sulfonic acid salt represented by the following general formula can also be preferably exemplified.

[0022] R 'O (R "O) a (CH 2) b SO 3 M ( wherein, R' is a monovalent hydrocarbon radical, R" is 2 carbon atoms
A to 4 alkylene groups, a is an integer of 1 to 100, b is 2 to
Integer of 4, M represents an alkali metal such as Na, K, Li, etc.) Among them, sodium dodecylbenzenesulfonate, a mixture of sodium alkylsulfonate having an average of 14 carbon atoms, C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₃ −
CH ₂ CH ₂ SO ₃ Na, C ₁₆ H ₃₃ O (CH ₂ CH
₂ O) Metal salts of sulfonic acids such as ₂₃ CH ₂ CH ₂ CH ₂ SO ₃ Na are good.

These organic metal salts may be used alone or in combination of two or more. Its amount C ₂ is 0.2 to 3 of the aromatic polyester constituting the core component of the sheath-core composite fibers
% By weight. If this amount is less than 0.2% by weight, sufficient antistatic properties cannot be imparted, and even if this amount exceeds 3% by weight, the antistatic properties are no longer remarkably improved. On the contrary, the fabric comprising the core-sheath type conjugate fiber is not preferable because the alkali weight loss rate, visual infectious color, pressure loss whitening property and the like are deteriorated.

The antistatic agent-containing core component described above further contains a hindered phenol-based, sulfide-based, phosphite-based antioxidant, or a benzophenone-based or benzotriazole-based ultraviolet absorber. This is preferred. For example, by blending an antioxidant, it is possible to suppress a decrease in antistatic property due to thermal decomposition of polyoxyalkylene glycol or a derivative thereof due to high temperature, low ejection speed, and long residence time in a fiber spinning process and the like. be able to. It is more preferable to mix these antioxidants and ultraviolet absorbers in advance with the above-described polyoxyalkylene glycol or a derivative thereof because the above-mentioned effects can be enhanced.

The above antioxidants may be used singly or as a mixture of two or more, and it is preferable to use them in a mixture. Further, the compounding amount of the antioxidant is preferably in the range of 0.02 to 3% by weight based on the aromatic polyester. This compounding amount is 0.02
When the amount is less than 3% by weight, the effect of inhibiting the thermal decomposition of the polyoxyalkylene glycol or a derivative thereof is insufficient. On the other hand, when the amount is more than 3% by weight, the effect of inhibiting the thermal decomposition is saturated and further improvement is not achieved. No, the mechanical properties, hue, etc. of the resulting fiber are impaired.

In addition, if necessary, the above-mentioned antioxidant and / or ultraviolet absorber may be blended with the sheath component of the polyester fiber of the present invention. Whitening agents, matting agents such as titanium oxide,
Coloring agents, colloidal silica, dry process silica, colloidal alumina, particulate alumina, inactive fine particles such as calcium carbonate and calcium phosphate, and any other additives may be blended.

In order to obtain a core component polyester containing the above-mentioned compounding agents, for example, the above-mentioned polyoxyalkylene glycol or a derivative thereof, an organic metal salt and, if necessary, the above-mentioned antioxidant and the like are added from the start of the polyester synthesis. At any time before the spinning step, they may be added separately or in advance by mixing.

Next, the intrinsic viscosity of the aromatic polyester as a sheath component of the conjugate fiber constituting the polyester fabric of the present invention must be 0.55 or more.
When [η] is less than 0.55, crystallization is easily caused by heat and the toughness tends to be inferior and brittle. Therefore, when the alkali weight reduction treatment with a weight loss rate of 10% or more is performed, the sheath component becomes fibril even by a weak mechanical frictional force. However, there are disadvantages such as insufficient wear resistance or insufficient mechanical properties such as tear strength. Further, the whitening phenomenon of weight loss at the pressure portion is also likely to occur. The pressure whitening phenomenon in this case is
Since the sheath component in which the antistatic agent is not dispersed is fragile due to pressure and fine cracks are easily generated, the sheath component is generated.
% Or more causes the elution of the core component, and a part of the filament has a hollow structure, so that the dyed cloth looks whitish.

The thickness of the sheath component of the conjugate fiber constituting the polyester fabric of the present invention must be in the range of 2 to 10 μm, and particularly preferably in the range of 3 to 8 μm. When the thickness of the sheath component is less than 2 μm, the fiber strength, fibril resistance, and the above-mentioned whitening defects of pressure loss become frequent, and the sheath cannot be put to practical use. Conversely, if the thickness of the sheath component exceeds 10 μm, the effect of the polyoxyalkylene glycol or its derivative and the organic metal salt blended in the core of the polyester fiber is not sufficiently exerted, resulting in poor antistatic properties. .

The core / sheath area composite ratio of the fibers constituting the polyester fabric of the present invention is in the range of 5/95 to 18/82, preferably 5/95 to 15/82. When the area composite ratio of the core / sheath exceeds 18/82, the above-mentioned weight loss whitening phenomenon at the pressure portion is apt to occur, and fibrillation is apt to occur due to mechanical friction. As the area composite ratio of the core / sheath increases, the whitening of the pressure loss and the occurrence of fibrillation become more severe, and the weight loss whitening phenomenon occurs at a very low pressure, and the fibrillation occurs with a very small friction. The object of the present invention is no longer achieved. For example, when the core / sheath area composite ratio exceeds 50/50, the polyester portion constituting the sheath component becomes extremely thin, and fiber strength, fibril resistance,
Physical properties such as heat resistance are inferior, and furthermore, the antistatic property after dyeing and its washing durability, as well as the color clarity and the fastness of the dyed product are not at an insufficient level, but also the above-described pressure loss whitening defect. Because it occurs frequently, it is not practical. On the other hand, the core / sheath area composite ratio is 5/95.
If it is less than 3, the effect of the polyoxyalkylene glycol or its derivative and the organic metal salt blended in the core of the polyester fiber is not sufficiently exhibited, and the antistatic property becomes poor. In addition, in the melt spinning process, the ejection speed on the core component side becomes low, and the core component stays at a high temperature for a long time, so that the polyoxyalkylene glycol or its derivative and the organic metal salt are easily thermally decomposed, and In addition to the decrease in the properties, the problem that the fibers are yellowed in the melt spinning step is likely to occur.

In the present invention, it has been found that it is still insufficient to satisfy the above requirements, and it is essential to satisfy the following requirements. That is, the compounding amount C of the polyoxyalkylene glycol or its derivative present in the core component of the fiber constituting the polyester fabric.
₁ (% by weight), the blending amount of the organic metal salt C ₂ (% by weight), the outer peripheral length L ₀ of the composite fiber in a cross section perpendicular to the fiber axis, and the outer peripheral length L of the figure formed by the core component
₁ must satisfy the following expression (3). (3) 2.2 ≦ (C ₁ + C ₂ ) × (L ₁ / L ₀ ) ^0.5 ≦ 5.0 In the above formula, (C ₁ + C ₂ ) × (L ₁ / L ₀ ) ^0.5
Is less than 2.2, the effect of the polyoxyalkylene glycol or its derivative and the organic metal salt blended in the core of the polyester fiber is not sufficiently exhibited, and the antistatic property becomes poor. Conversely, (C ₁ + C ₂ ) × (L ₁ / L
₀ ) Even if ^0.5 exceeds 5.0, no further improvement effect on the antistatic property of the obtained polyester fabric is recognized, and the mechanical properties, heat resistance,
Light resistance and the like are impaired. In addition, since the interfacial adhesiveness between the core and the sheath is reduced, the above-mentioned whitening phenomenon of the pressure portion is easily caused, and fibrillation is easily caused by mechanical friction. As the value of (C ₁ + C ₂ ) × (L ₁ / L ₀ ) ^0.5 increases, the pressure loss whitening and fibrillation become severe, and the weight loss whitening phenomenon occurs at a very low pressure, and the fibrillation occurs with a very small friction. Therefore, the object of the present invention cannot be achieved. (C ₁ + C ₂ ) × (L ₁ / L ₀ )
^{More preferably,} the value of ^0.5 is 2.5 to 4.0.

Further, the cross-sectional shape of the outer periphery of the conjugate fiber constituting the antistatic polyester fabric of the present invention and the shape of the figure formed by the core component may be such as bulkiness, tension, waist, feeling, gloss and the like of the woven or knitted fabric. Any shape can be taken according to the purpose, for example, in addition to a circular cross section, triangular, flat, square, pentagonal,
Examples include a star shape, a hexagon, and a boomerang type. Further, the core component and the sheath component do not need to be concentric, and may have a shape in which the center of the core is deviated.Also, the cross-sectional shape of the outer periphery and the shape of the figure formed by the core component are the same shape. Or different shapes.

The fibers constituting the antistatic polyester fabric of the present invention are prepared by using a conventionally known composite spinning apparatus, wherein the above-described aromatic polyester is provided on the sheath side, and polyoxyalkylene glycol or a derivative thereof and an organic metal salt are provided on the core side. In addition, by using an aromatic polyester to which an antioxidant is blended if necessary, it can be produced without any trouble under arbitrary thread-making conditions. For example, a method of melt-spinning at a speed of 500 to 2500 m / min, stretching and heat treatment, 1500 to 5000
melt spinning at a speed of m / min, and simultaneous or subsequent stretching and false twisting; melt spinning at a high speed of 5000 m / min or more; Conditions can be adopted. Further, the obtained fiber or a woven or knitted fabric produced from this fiber is subjected to a heat treatment at a temperature of 100 ° C. or more to stabilize the structure and polyoxyethylene-based polyether contained in the fiber, and if necessary, It is also preferable to promote proper alignment by transfer of various additives contained therein. Further, relaxation heat treatment or the like can be used as needed.

In the present invention, a cloth made of the antistatic polyester composite fiber alone described above in detail or a cloth made by weaving and knitting with other fibers is subjected to alkali weight reduction processing.
As the other fibers used here, not only ordinary polyester fibers but also any fibers such as polyamide fibers and rayon fibers can be used. Among them, polyester fibers have a good feeling of fabric improvement by alkali weight reduction processing. So more preferred. If the interweaving / knitting ratio of the other fibers is too large, the antistatic performance aimed at by the present invention is reduced. Therefore, the ratio of the antistatic polyester composite fiber is 90% or less, in other words, the ratio of the antistatic polyester composite fiber is 10% or more. Is desirable.

In the alkali weight reduction processing, an aqueous solution containing an alkali is used, and at least 10% weight reduction treatment is carried out according to a conventional method. The purpose of the present invention is achieved only when the composite fibers constituting the fabric after the alkali weight reduction process satisfy the above requirements.

The alkali used in the alkali reduction treatment refers to an alkali that can hydrolyze and dissolve the polyester fiber, such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, sodium carbonate, potassium carbonate and the like. . Among these alkalis, it is particularly preferable to use sodium hydroxide and potassium hydroxide. Further, an alkali weight loss promoter such as cetyltrimethylammonium bromide and lauryldimethylbenzylammonium chloride may be added to the aqueous alkali solution. The alkali reduction treatment can be easily performed by a method such as immersing the object to be treated in the aqueous solution of alkali or impregnating the object with the aqueous solution of alkali and subjecting the object to steam heat treatment. The concentration of the aqueous alkali solution varies depending on the type of alkali, treatment conditions, and the like, but is usually 0.01%.
It is preferably in the range of from about 40% by weight to about 40% by weight.
More preferably, it is in the range of 1 to 30% by weight. The alkali reduction treatment temperature is preferably in the range of room temperature to 160 ° C.

The antistatic polyester fabric of the present invention may be subjected to appropriate post-hydrophilization processing, and it is preferable to do so. As the post-hydrophilization processing, for example, a method of treating with an aqueous dispersion of a polyester polyether block copolymer composed of terephthalic acid and / or isophthalic acid or a lower alkyl ester thereof, a lower alkylene glycol, and a polyalkylene glycol. Alternatively, a method in which a hydrophilic monomer such as acrylic acid or methacrylic acid is graft-polymerized, and then the resultant is converted into a sodium salt can be preferably employed.

[0038]

The antistatic polyester fabric of the present invention has excellent antistatic properties and is not affected by repeated washing treatments. Furthermore, weight loss rate 30%
Even when high alkali weight loss treatment is applied, woven and knitted products have no pressure loss whitening defects and have excellent fibril resistance and abrasion resistance in each step, so lingerie etc. It can be used not only in the fields of women's inner use, lining, dust-free clothing, etc., but also as an antistatic surface material with a high degree of improved hand feeling by alkali weight reduction treatment.

[0039]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Parts and% in Examples and Comparative Examples
Represents parts by weight and% by weight, respectively. Further, the frictional electrostatic voltage, the core / sheath configuration after weight loss, the abrasion resistance, and the pressure whitening resistance of the weight loss dyed fabric of the obtained antistatic polyester fabric were measured by the following methods.

(1) Friction band voltage The knitted fabric is refined by a conventional method and preset (at 180 ° C.).
× 1 minute), the alkali was reduced at the boiling temperature with a 30 g / liter aqueous sodium hydroxide solution,
mikalon Navy Blue S-2GL (manufactured by Sumitomo Chemical Co., Ltd.) 4% owf, Disper VG (manufactured by Meisei Chemical Industry Co., Ltd.) 0.5 g / l and acetic acid 0.3 g / l in a dye bath containing 1/5 bath ratio.
After staining at 130 ° C. for 60 minutes at 0 ° C., sodium hydroxide 1
The resultant was reduced and washed with an aqueous solution containing g / liter and hydrosulfite at 1 g / liter at 70 ° C. for 20 minutes and further subjected to a final set (160 ° C. × 1 minute) by a conventional method (dyed knitted fabric A). This dyed knitted fabric A is JIS L-1018-77
According to the 6.36H method, washing was carried out for 30 times of washing (referred to as L30) (dyeed knitted fabric B). These dyed knitted fabrics A and B were allowed to stand in a desiccator at 40 ± 2% RH for one day or more to adjust the humidity to obtain test pieces.

In a room having an atmosphere of 40 ± 2% RH and 20 ± 2 ° C., a triboelectric voltage was measured according to JIS L-1094 8.2B method using a rotary static tester (Kyoto Univ., Kaken formula). If the friction band voltage is 1.5 kV or less, an antistatic effect can be obtained.

(2) Structure of core / sheath after weight reduction The yarn cross section of the weight-reduced dyed knitted fabric A obtained above was observed with an optical photograph or a transmission electron micrograph if necessary, and the thickness of the sheath component, the fiber the length L ₀ of the outer periphery of the length L ₁ of the outer periphery of a graphic core components form was measured core / sheath area composite ratio.

(3) Abrasion resistance A twisted yarn of 300 T / m is woven into a plain weave at a warp density of 43 yarns / cm and a weft density of 40 yarns / cm as warp yarns. After that, pre-setting was carried out, followed by alkali reduction treatment at a boiling temperature with a 30 g / L aqueous sodium hydroxide solution, and dyeing and final setting were carried out in the same manner as described above to finish. Five circular test pieces having a diameter of 13 cm were collected from the obtained woven fabric, and a hole having a diameter of about 6 mm was formed at the center of each test piece, and a Taber type friction tester (JIS L-1096) was used.
C method), the test piece was mounted on the rubber mat of the sample holder with the surface of the test piece facing up, and a wear wheel (CS-10: 250 g) was used.
f) is placed on a test piece and subjected to rotational friction at about 70 times per minute, and the appearance after 50 times of friction is observed. The following judgment is made, and Class A and Class AB are practically usable. Judged as level.

Class A: No abnormality Class A to B: Very slightly damaged Class B: Slightly damaged Class C: Cut in warp or weft (4) Pressure-resistant whitening resistance of weight-reduced dyed cloth The evaluation was made by the following two methods, a calendar method and a pencil mark method.

(I) Calendering Method The knitted fabric obtained by scouring and presetting the knitted fabric by a conventional method is passed between calender rolls with a linear pressure of 50 kg / cm, and then subjected to alkali reduction, dyeing, final Each treatment of the set was performed to obtain a weight-loss dyed knitted fabric C. The L ^* value (brightness index) of the weight loss dyed knitted fabric A and the weight loss dyed knitted fabric C was measured using Macbeth MS-2020 (Instrumental Color System Limited).
And the difference between the two L ^* values (ΔL ^* ),
The degree of pressure whitening resistance was evaluated. ΔL ^* = L ^* (knitted fabric C) −L ^* (knitted fabric A) A smaller ΔL ^* value indicates that the pressure-resistant whitening resistance of the weight-reduced dyed cloth is excellent, and ΔL ^* ≦ 2.0. is necessary.

(Ii) Pencil Mark Method A knitted fabric obtained by scouring and presetting a knitted fabric by a conventional method is applied with a HB pencil in a grid pattern at intervals of 1 cm (approximately 300).
g), and each of the treatments of alkali weight loss, dyeing, and final setting was performed to obtain a weight-loss dyed knitted fabric D. The dyeing difference between the pencil mark portion of the weight-loss dyed knitted fabric D and the cloth to which pressure was not applied was visually observed, and the following judgment was made, and お よ び and △ to と were judged to be practically usable levels.

[0047] ○ Senshokusa is not observed ○ ~ △ be of ΔL ^* ≦ 2.0 in a very slightly stained difference is observed △ slightly calendar method × clear staining difference Senshokusa are found are found, pencil In some mark methods, a difference in dyeing is observed, and the pencil mark method is a more severe evaluation method for pressure whitening resistance than the calender method.

[0048]

Examples 1 to 7 and Comparative Examples 1 to 5 100 parts of dimethyl terephthalate, 60 parts of ethylene glycol, 0.06 part of calcium acetate monohydrate (0.066 mol% based on dimethyl terephthalate) and a color stabilizer As cobalt acetate 4
0.009 parts of water salt (0.1 part based on dimethyl terephthalate)
(007 mol%) in a transesterification vessel, and the mixture was heated from 140 ° C. to 220 ° C. over 4 hours in a nitrogen gas atmosphere to carry out a transesterification reaction while distilling off the generated methanol to the outside of the system. After the transesterification reaction, 0.058 parts of trimethyl phosphate (0.080 mol% based on dimethyl terephthalate) as a stabilizer and 0.024 parts of dimethylpolysiloxane as an antifoaming agent were added to the reaction mixture. Then, 10 minutes later, 0.04 parts of antimony trioxide (0.027 mol% based on dimethyl terephthalate) was added, and at the same time, 240 ° C.
After the temperature was raised, the mixture was transferred to a polymerization reactor. Next, polyethylene glycol (average molecular weight: 20,000) was added in the amount shown in (Table 1), and then the pressure in the reactor was reduced from 760 mmHg to 3 mmHg over 1 hour.
Ten minutes after reaching Hg, sodium alkylsulfonate having an average carbon number of 12 to 13 (abbreviated as DS) as an organic metal salt was added under reduced pressure in an amount described in (Table 1). The pressure was further reduced to 1 mmHg, and at the same time, the temperature of the reaction mixture was raised from 240 ° C to 280 ° C over 1 hour and 30 minutes. The polymerization was further carried out at a polymerization temperature of 280 ° C. under a reduced pressure of 1 mmHg or less at 280 ° C. for 2 hours. At this stage, 0.1 parts of Cyanox 1790 (manufactured by American Cyanamid Co.) and ADK STAB AO-412S as antioxidants were added to the reaction mixture.
0.3 parts (manufactured by Adeka Argus Chemical Co., Ltd.) was added under reduced pressure, and thereafter polymerization was carried out for 30 minutes. The intrinsic viscosity of the obtained polymer was in the range of 0.635 to 0.645, and the softening point was in the range of 260 to 263 ° C. This polymer was formed into chips by a conventional method.

The thus obtained aromatic polyester containing polyethylene glycol and an organic metal salt was used as a core component polymer, dried by a conventional method, melted by a screw type extruder, and supplied to a two-component composite spinning head via a gear pump. . On the other hand, as a polymer for a sheath component, a polyethylene terephthalate chip having an intrinsic viscosity of a value described in (Table 1) is dried by a conventional method and then melted by a screw type extruder.
Similarly, it was fed to a composite spinning head. The supply amounts of the polymer for the core component and the polymer for the sheath component were set such that the area ratio of the core component became the value described in (Table 1). Simultaneously supplied molten polymer of core component and sheath component, nozzle diameter 0.3mm
Was extruded at 285 ° C. using a composite spinneret in which 36 circular composite spinning holes were formed, and was once wound up at a speed of 1500 m / min through a goded roll. Then, at a draw ratio such that the elongation of the obtained drawn yarn becomes 35%, 90
A drawing heat treatment was performed with a heating roller at 170 ° C. and a drawing heater at 170 ° C. to obtain a drawn yarn of 75 denier / 36 filaments.

The obtained drawn yarn was made into a knitted fabric, and the knitted fabric A was subjected to scouring, presetting, alkali weight reduction (weight reduction rate shown in Table 1), dyeing, and final setting by the above-described method.
(0 washing times: referred to as L ₀ ) and the frictional electrostatic voltage of the dyed knitted fabric B after 30 times of washing (referred to as L ₃₀ ) were measured. The dyed knitted fabric C subjected to scouring, presetting, calendering, alkali weight reduction (weight loss rate shown in Table 1), dyeing, and final setting, and the dyed knitted fabric D similarly treated by applying a pressure with a pencil mark instead of the calendar ,
The pressure loss whitening resistance was evaluated. Further, the greige fabric obtained by weaving in a plain weave as described above was evaluated for abrasion resistance of a woven fabric which was subjected to scouring, presetting, alkali weight loss (weight loss rate shown in Table 1), dyeing, and final setting. The results are shown in (Table 1).

[0051]

Examples 8 to 9 and Comparative Example 6 The same operation as in Example 2 was performed. However, the supply amounts of the polymer for the core component and the polymer for the sheath component to be supplied to the two-component composite spinning head are set so that the area ratio of the core component becomes the value described in (Table 1). 75 denier / 24 filaments (Example 8), 150 denier / 24 filaments (Example 9), 200 denier / 24 filaments (Comparative Example 6) using a composite spinneret having 24 composite spin holes ) Was obtained, and the knitted fabric and the woven fabric were evaluated. The results are shown in (Table 1).

[0052]

Example 10 The same operation as in Example 2 was performed. However, the molten polymer of the core component and the sheath component has a nozzle diameter of 0.15 mm.
Using two composite spinnerets in which 72 circular composite spinning holes were drilled, melt-spinning was performed at 1500 m / min, followed by drawing heat treatment, and then mixed to obtain a drawn yarn of 64 denier / 144 filaments. The knitted fabric and the woven fabric were evaluated.
The results are shown in (Table 1).

[0053]

Example 11 The same operation as in Example 2 was performed. However, instead of polyethylene glycol having an average molecular weight of 20,000, polyethylene glycol having an average molecular weight of 8,000 was used, and instead of sodium alkyl sulfonate having an average carbon number of 12 to 13 as an organic metal salt, sodium dodecylbenzene sulfonate ( DBS). The results are shown in (Table 1).

[0054]

Examples 12 and 13 The same operation as in Example 11 was performed.
However, instead of polyethylene glycol having an average molecular weight of 8,000, the chemical formula HO- (CH (C _j H _{2j + 1} ) CH _{2
O-) m - (CH 2 CH} 2 O-) p - (CH 2 CH (C
_{j H 2j + 1) O-)} m -H ( where, m is 3 as an average value,
p is an average value of 115, j is an integer of 18 to 28 and an average of 21), and is a polyethylene glycol derivative having an average molecular weight of 7106 (abbreviated as polyether A).
Was used. The results are shown in (Table 1).

[0055]

Example 14 The same operation as in Examples 12 and 13 was performed.
However, instead of sodium dodecylbenzenesulfonate as an organic metal salt, the chemical formula C ₁₂ H ₂₅ O (CH ₂ CH ₂
O) ₃ abbreviated as _{-CH 2 CH 2 SO 3 Na (} MS) was used. The results are shown in (Table 1).

[0056]

Example 15 The same operation as in Example 11 was performed. However,
Instead of polyethylene glycol having an average molecular weight of 8,000, the chemical formula HO— (CH ₂ CH ₂ O—) _m — (CH
_{(CH 3) CH 2 O-)} p (CH 2 CH 2 O-) n -H
(Where m and n are each about 129 as an average value, and p is about 35 as an average value).
3300 polyoxyethylene polyoxypropylene block polymer (abbreviated as polyether B) was used. The results are shown in (Table 1).

[0057]

Example 16 The same operation as in Example 11 was performed. However,
Instead of polyethylene glycol having an average molecular weight of 8,000, the chemical formula HO— (CH ₂ CH ₂ O—) _m — (CH
_{(CH 3) CH 2 O-)} p - (CH 2 CH 2 O-) n -
H (where m and n are respectively about 77 as an average value and p is about 21 as an average value) 8
000 polyoxyethylene polyoxypropylene block polymer (abbreviated as polyether C) was used.
The results are shown in (Table 1).

[Table 1]

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Toyoshi Suzuki 77 Kitayoshida-cho, Matsuyama-shi, Ehime Prefecture Teijin Limited Matsuyama Office (56) References JP-A-56-154534 (JP, A) JP-A-4 -146268 (JP, A) JP-B-61-6883 (JP, B2) JP-B-63-17927 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) D03D 15/00 D03D 15/00 101 D01F 1/09 D01F 8 / 14A

Claims (1)

(57) [Claims] 1. A fabric comprising a core-sheath conjugate fiber in which both core-sheath components are made of aromatic polyester and a weight loss rate of 10% or more has been subjected to alkali weight reduction. A polyoxyalkylene glycol or a derivative thereof which is substantially non-reactive with the aromatic polyester, and (b) an organometallic salt, wherein the intrinsic viscosity of the aromatic polyester of the sheath component is 0.55 or more and the thickness of the sheath component is 2-10
μm and the core / sheath area composite ratio is 5 /
95-18 / 82, the blending amount C ₁ (% by weight) of the polyoxyalkylene glycol or its derivative present in the core component, the blending amount C ₂ (% by weight) of the organic metal salt,
The outer peripheral length L ₀ of the composite fiber in a cross section perpendicular to the fiber axis, and the outer peripheral length L of the figure formed by the core component
₁ is an antistatic polyester fabric excellent in abrasion resistance, wherein the following formulas (1) to (3) are simultaneously satisfied. (1) 2.0 ≦ C ₁ ≦ 7.0 (2) 0.2 ≦ C ₂ ≦ 3.0 (3) 2.2 ≦ (C ₁ + C ₂ ) × (L ₁ / L ₀ ) ^0.5 ≦
5.0