JP2008240201A - Method for producing copolyester fiber excellent in light resistance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing copolyester fibers which are excellent in functional properties such as hygroscopicity, water absorbability and quick dryness and little cause the deterioration of the functional properties (especially hygroscopicity) with the exposure of solar light. <P>SOLUTION: This method for producing the copolyester fibers having the characteristics is characterized by treating fibers comprising a copolyester containing a polyalkylene terephthalate as a main constituting component and copolymerized with a polyether component in the side chains of the polyester and further copolymerized with a specific metal organic sulfonate in the polyester, with a water-soluble salt of a metal selected from nickel, manganese and barium to at least partially replace the metal of the metal sulfonate in the copolymer by nickel, manganese and barium. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a copolyester fiber having excellent light resistance. More specifically, it has excellent hygroscopicity, water absorption and quick-drying properties, has outstanding heat conductivity and moisture permeability that has never been seen before, and expresses a refreshing and cool feeling that surpasses natural fibers such as cotton and linen. In addition, the invention relates to a method for industrially producing a copolyester fiber excellent in light resistance, with little decrease in functionality such as hygroscopicity, water absorption, thermal conductivity, and moisture permeability associated with sun exposure. is there.

  Polyester has been widely used as a synthetic fiber since it has many excellent properties. However, since polyester fibers are hydrophobic, they have the disadvantage that their water absorption and hygroscopicity are significantly inferior compared to natural fibers such as cotton and linen, and their use is limited in fields where water absorption and hygroscopicity are required. Has been. In particular, the use of polyester fibers in clothing applications where the fabric is in direct contact with the skin is extremely limited because it causes significant discomfort such as stuffiness and stickiness, especially in midsummer clothing applications. The use of is virtually none.

  Conventionally, in order to solve this problem, many attempts have been made to impart water absorbency and moisture absorbency to polyester fibers. For example, as a method for imparting water absorption (property of absorbing water in a liquid state) to a polyester fiber, there are a method for modifying the fiber surface to impart water absorption and a method for increasing water absorption to the inside of the fiber. The former method mainly employs a method in which the surface of the fiber is covered with a hydrophilic compound by modifying the raw yarn or post-processing. In addition to this, discharge treatment, photografting, etching with chemicals, low temperature of the hydrophilic compound are used. Plasma polymerization processing etc. As the latter method, the water absorption is increased by making the polyester fiber porous by utilizing a capillary phenomenon.

  However, these methods have a corresponding effect in the sensed digestion, that is, in the state of sweating, and in particular for porous water-absorbing polyester fibers, the water retention rate and the moisture perception limit (the water retention rate that can be felt wet) are reduced. The effect of remarkably enhancing is obtained and it has a quick drying property, so that it can absorb a lot of sweat and exert a comfortable sweat treatment function in sports applications, etc., but has a hygroscopic property (the ability to absorb water in a vapor phase, that is, water vapor). Because there is almost no, there is no special effect on insensitive digestion that is constantly evaporating outside the body without reaching the human sense, and there is little effect to eliminate the feeling of stuffiness and heat It is far from the coolness and coolness of natural fibers such as cotton and linen. In addition, in the method of forming a hydrophilic resin film on the surface of the fiber, the hydrophilic film is formed only on the surface of the hydrophobic fiber, and since the affinity between the two is poor, the washing durability is poor. There are drawbacks.

  On the other hand, a post-processing method by graft polymerization of a hydrophilic compound has been proposed as a method for imparting hygroscopicity to a polyester fiber. According to this method, for example, a moisture absorption rate equivalent to that of cotton can be obtained by graft-polymerizing acrylic acid or methacrylic acid to polyethylene terephthalate fiber by about 15% by weight and then sodium chloride treatment. However, although the hygroscopic polyester fiber modified by such graft polymerization certainly has an equilibrium moisture absorption rate similar to that of cotton, the moisture absorption rate up to the equilibrium moisture absorption rate is significantly lower than that of cotton. In connection with this, there is little effect to eliminate the stuffiness and stickiness when worn, and a refreshing feeling cannot be obtained. In addition, this method has disadvantages such as a decrease in dyeing fastness of the fiber and curing of the texture, so that it cannot be put into practical use.

  On the other hand, as the polyester which made the polymer itself hygroscopic, there is no remarkable thing other than the polyester which copolymerized polyoxyethylene glycol conventionally known. Although the polyester containing such a polyoxyethylene glycol component exhibits a hygroscopic improvement effect, the improvement effect is relatively small. Therefore, a large amount of polyoxyethylene glycol component is required, and as a result, a modified polyester fiber finally obtained Its physical properties and heat resistance are markedly reduced, and its practical value is low.

  As another means for improving the drawbacks of the polyoxyethylene glycol copolymer polyester, a method for producing a copolymer polyester having a polyoxyethylene glycol component in the side chain with respect to the polyester polymer main chain has been proposed (see below). (See Patent Document 1 and Patent Document 2). According to this method, by introducing a relatively small amount of the polyoxyethylene glycol component, when formed into a fiber, it is excellent in hygroscopicity, water absorption and quick drying, and has good thermal conductivity and moisture permeability. It is said that it is useful because a copolyester exhibiting a cool feeling and cool feeling can be obtained. However, the fiber made of a copolyester having a polyoxyethylene glycol component in the side chain with respect to the polyester polymer main chain is as described above in the field of use outdoors such as being exposed to sunlight for a long time. It has been found that there may be a problem that the functionality such as excellent hygroscopicity and water absorption is lowered.

Japanese Examined Patent Publication No. 6-84426 Japanese Patent Publication No. 6-84427

  The present invention has been made in view of the above-described background art, and its purpose is to eliminate the problem that the above-described copolymer polyester fiber is deteriorated by exposure to sunlight, and to absorb moisture, absorb water, and quickly dry. It has excellent heat conductivity and moisture permeability that are unprecedented, and can express a refreshing feeling and cooling feeling that surpasses natural fibers such as cotton and linen. It is an object of the present invention to provide a method for producing a copolyester fiber that is less deteriorated in properties and excellent in light resistance.

  As a result of various studies on the copolymerized polyester fiber in order to achieve the above object, the present inventor has copolymerized a specific organic sulfonic acid metal salt with a polyester in which the polyether component is copolymerized in the side chain. By treating the copolyester fiber with a specific water-soluble metal salt, the copolyester fiber finally obtained exhibits excellent functionality such as hygroscopicity, water absorption, thermal conductivity, moisture permeability, It has been found that the decrease in functionality due to exposure to sunlight can be remarkably prevented and the above-mentioned problems can be achieved. The present invention has been completed as a result of further studies based on these findings.

  That is, the above-mentioned object of the present invention is achieved by the following method for producing a copolyester fiber of the present invention.

[1] A polyester having polyalkylene terephthalate as a main structural unit, wherein a polyether component is copolymerized in the side chain of the polyester, and the organic sulfonic acid represented by the following general formula (1) in the polyester A method for producing a copolyester fiber excellent in light resistance, characterized by treating a fiber comprising a copolyester having a metal salt copolymerized with a water-soluble metal salt of a metal selected from nickel, manganese and barium .

[2] The above-mentioned [1], wherein the polyether component copolymerized in the side chain is a diol compound represented by the following general formula (2) and / or an epoxy compound represented by the following general formula (3) ] The manufacturing method of the copolyester fiber excellent in light resistance of description.

[3] The light resistance as described in [1] or [2] above, wherein the polyether component copolymerized in the side chain is 0.5 to 50% by weight based on the copolymerized polyester. A method for producing a copolyester fiber.

[4] The above [1] to [3], wherein the copolymerization amount of the organic sulfonic acid metal salt is 0.5 to 20 mol% with respect to the bifunctional carboxylic acid component constituting the copolymer polyester. ] The manufacturing method of the copolyester fiber excellent in light resistance in any one of.

  According to the method of the present invention, it is excellent in hygroscopicity, water absorption and quick drying, has extremely superior thermal conductivity and moisture permeability, and has a refreshing feeling / cooling superior to natural fibers such as cotton and hemp. A polyester fiber can be produced which can express a feeling and is less susceptible to the above-described decrease in functionality due to exposure to sunlight. Therefore, fiber structures and fiber products such as woven and knitted fabrics and non-woven fabrics containing copolymerized polyester fibers obtained by the present invention are extremely useful particularly in apparel applications such as the field of sportswear and the field of midsummer wear used outdoors.

  The base polyester constituting the copolymerized polyester fiber of the present invention comprises terephthalic acid as a main difunctional carboxylic acid component, and at least one alkylene selected from at least one glycol, ethylene glycol, trimethylene glycol, and tetramethylene glycol. The main object is polyester (alkylene terephthalate polyester) having glycol as a glycol component.

  The polyester is a polyester in which a part of the terephthalic acid component is replaced with another difunctional carboxylic acid component and / or a polyester in which a part of the glycol component is replaced with the glycol or other diol component other than the main component. Also good.

  Examples of the bifunctional carboxylic acid other than terephthalic acid used here include isophthalic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, and adipic acid. And aromatic, aliphatic and alicyclic bifunctional carboxylic acids such as sebacic acid and 1,4-cyclohexanedicarboxylic acid.

  Examples of the diol compound other than the glycol include aliphatic, alicyclic, and aromatic diol compounds such as cyclohexane-1,4-dimethanol, neopentyl glycol, bisphenol A, and bisphenol S.

  Furthermore, polycarboxylic acids such as trimellitic acid and pyromellitic acid, and polyols such as glycerin, trimethylolpropane, and pentaerythritol can be used within the range where the polyester is substantially linear.

  Such polyester is synthesized by any method. For example, for polyethylene terephthalate, terephthalic acid and ethylene glycol are usually esterified directly, terephthalic acid lower alkyl ester such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid and ethylene oxide. In the first step to produce a glycol ester of terephthalic acid and / or its low polymer, and the reaction product in the first step is heated under reduced pressure until the desired degree of polymerization is reached. It is produced by a second stage reaction that causes a condensation reaction.

  The copolymerized polyester used in the present invention is obtained by copolymerizing a polyether component on the side chain of the base polyester. The polyether component is preferably a polyoxyalkylene component. For example, a copolymer obtained by copolymerizing the base polyester with a diol compound represented by the following general formula (2) and / or an epoxy compound represented by the following general formula (3). Polymerized polyester can be given as a preferred specific example.

In these formulas, R ₁ and R ₁ ^′ each represent a hydrocarbon group, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or An alkylaryl group having 8 to 16 carbon atoms is preferred. R ₂ and R ₂ ^′ are alkylene groups, preferably alkylene groups having 2 to 4 carbon atoms. Specific examples include an ethylene group, a propylene group, and a tetramethylene group. In addition, a random copolymer or a block copolymer having, for example, an ethylene group and a propylene group, or an ethylene group and a tetramethylene group, in which two or more alkylene groups are mixed may be used. m and m ′ are positive integers indicating the degree of polymerization, and are preferably in the range of 30 to 140. If the degree of polymerization is less than 30, the sufficient hygroscopicity, moisture permeability, and refreshing / cooling feeling of natural fibers such as cotton and hemp are not exhibited, and the object of the present invention is not achieved. On the other hand, when the degree of polymerization exceeds 140, copolymerization becomes difficult, and sufficient hygroscopicity / humidity, refreshing feeling, and cooling feeling are not exhibited. Among these, a particularly excellent hygroscopicity / moisture permeability is exhibited in a polymerization degree range of 40 to 100, and a refreshing feeling and a cool feeling are particularly remarkable, which is preferable. Note that R ₁ and R ₁ ^′ , R ₂ and R ₂ ^′ , m and m ′ in the above formulas may be the same or different from each other.

  Preferable specific examples of the compound serving as the polyether component include polyoxyethylene glycol methyl 1,2-dihydroxypropyl ether, polyoxyethylene glycol phenyl 1,2-dihydroxypropyl as the diol compound represented by the above formula (2). Ether, polyoxyethylene glycol isopropyl 1,2-dihydroxypropyl ether, polyoxyethylene glycol n-butyl 1,2-dihydroxypropyl ether, polyoxyethylene glycol octylphenyl 1,2-dihydroxypropyl ether, polyoxyethylene glycol nonylphenyl 1,2-dihydroxypropyl ether, polyoxyethylene glycol cetyl 1,2-dihydroxypropyl ether, polyoxypropylene glycol Methyl 1,2-dihydroxypropyl ether, polyoxypropylene glycol phenyl 1,2-dihydroxypropyl ether, polyoxypropylene glycol n-butyl 1,2-dihydroxypropyl ether, polyoxypropylene glycol octylphenyl 1,2-dihydroxypropyl ether , Polyoxypropylene glycol nonylferni 1,2-dihydroxypropyl ether, polyoxytetramethylene glycol methyl 1,2-dihydroxypropyl ether, polyoxyethyl glycol / polyoxypropylene glycol copolymer methyl 1,2-dihydroxypropyl Examples include ethers, and among these, polyoxyethylene glycol derivatives are particularly preferable. The above diol compounds may be used alone or in combination of two or more.

  Preferred specific examples of the epoxy compound represented by the above formula (3) include polyoxyethylene glycol methyl glycidyl ether, polyoxyethylene glycol phenyl glycidyl ether, polyoxyethylene glycol isopropyl glycidyl ether, polyoxyethylene glycol n-butyl. Glycidyl ether, polyoxyethylene glycol octylphenyl glycidyl ether, polyoxyethylene glycol nonylphenyl glycidyl ether, polyoxyethylene glycol cetyl glycidyl ether, polyoxypropylene glycol methyl glycidyl ether, polyoxyethylene glycol phenyl glycidyl ether, polyoxyethylene glycol n -Butyl glycidyl ether, polyoxyethylene glycol Octyl phenyl glycidyl ether, polyoxyethylene glycol nonylphenyl glycidyl ether, polyoxy tetramethylene glycol methyl glycidyl ether, methyl glycidyl ether of polyoxyethylene glycol / polyoxypropylene glycol copolymer. Of these, polyoxyethylene glycol derivatives are particularly preferred. The said epoxy compound may be used individually by 1 type, and may use 2 or more types together.

  In order to copolymerize the above diol compound and / or epoxy compound with the above-described base polyester, any stage until the synthesis of the polyester described above is completed, for example, before the start of the first stage reaction, during the reaction, after the completion of the reaction It may be added at any stage such as during the second stage reaction, and the polycondensation reaction may be completed after the addition. At this time, if the amount used is too small, the finally obtained copolymer polyester fiber has insufficient moisture absorption / moisture permeability and refreshing / cooling performance. The improvement in wettability, coolness, and coolness performance is not seen, and the physical properties of the copolyester fiber finally obtained are deteriorated and the heat resistance and light resistance are deteriorated. The range is preferably 0.5 to 50% by weight, more preferably 10 to 40% by weight, and particularly preferably 15 to 30% by weight with respect to the polymerized polyester.

  In the present invention, an organic sulfonic acid metal salt represented by the following general formula (1) must be copolymerized with the copolymer polyester. By the copolymerization of the organic sulfonic acid metal salt, moisture absorption, water absorption, thermal conductivity, moisture permeability, cool feeling, cool feeling, etc. accompanying outdoor sunlight exposure of the finally obtained copolymer polyester fiber Decrease in functionality is suppressed.

上記一般式（１）式において、Ｒは芳香族炭化水素基又は脂肪族炭化水素基であり、好ましくは炭素数６〜１５の芳香族炭化水素基又は炭素数１０以下の脂肪族炭化水素基である。特に好ましいＲは炭素数６〜１２の芳香族炭化水素基、とりわけベンゼン環である。また、Ｘ_１はエステル形成性官能基を示し、Ｘ_２はＸ_１と同一もしくは異なるエステル形成性官能基あるいは水素原子を示すが、エステル形成性官能基であるのが好ましい。エステル形成性官能基としては、側鎖共重合型ポリエステルの主鎖又は末端に反応して結合する基であればよく、具体的には下記の基を挙げることができる。

In the above general formula (1), R is an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aromatic hydrocarbon group having 6 to 15 carbon atoms or an aliphatic hydrocarbon group having 10 or less carbon atoms. is there. Particularly preferred R is an aromatic hydrocarbon group having 6 to 12 carbon atoms, particularly a benzene ring. X ₁ represents an ester-forming functional group, and X ₂ represents the same or different ester-forming functional group or hydrogen atom as X ₁ , but is preferably an ester-forming functional group. The ester-forming functional group may be any group that reacts and binds to the main chain or terminal of the side-chain copolymerized polyester, and specific examples thereof include the following groups.

  Further, M in the general formula (1) is at least one metal selected from the group consisting of alkali metals and alkaline earth metals other than barium. When M is an alkali metal, n in the formula is 1, and when M is an alkaline earth metal (except barium), n is 2.

  Preferable specific examples of the organic sulfonic acid metal salt represented by the general formula (1) include 3,5-dicarbomethoxybenzene as a preferable specific example of the organic sulfonic acid metal salt represented by the general formula (1). Sodium sulfonate, potassium 3,5-dicarbomethoxybenzenesulfonate, lithium 3,5-dicarbomethoxybenzenesulfonate, sodium 3,5-dicarboxybenzenesulfonate, potassium 3,5-dicarboxybenzenesulfonate, Lithium 3,5-dicarboxybenzenesulfonate, sodium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate, potassium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate, 3,5-di (Β-Hydroxyethoxycarbonyl) benzenesulfonic acid Lithium, sodium 2,6-dicarbomethoxynaphthalene-4-sulfonate, potassium 2,6-dicarbomethoxynaphthalene-4-sulfonate, lithium 2,6-dicarbomethoxynaphthalene-4-sulfonate, 2,6 -Sodium dicarboxynaphthalene-4-sulfonate, 2,6-dicarbomethoxysphthalene-1-sodium sulfonate, 2,6-dicarbomethoxynaphthalene-3-sodium sulfonate, 2,6-dicarbomethoxynaphthalene Examples include sodium 4,8-disulfonate, sodium 2,6-dicarboxynaphthalene-4,8-disulfonate, sodium 2,5-bis (hydroethoxy) benzenesulfonate, α-sodium sulfosuccinic acid, and the like. . The said organic sulfonic acid metal salt may be used individually by 1 type, or may be used together 2 or more types.

  The copolymerization amount of the organic sulfonic acid metal salt is preferably in the range of 0.5 to 20 mol%, more preferably in the range of 1.0 to 10 mol% with respect to the bifunctional carboxylic acid component constituting the copolymerized polyester. More preferably, it is in the range of 1.5 to 7 mol%. If the amount of copolymerization of the organic sulfonic acid metal salt is too small, the effect of improving the light resistance of the resulting fiber will be insufficient. On the other hand, when the copolymerization amount of the organic sulfonic acid metal salt is too large, the melting point of the copolymerized polyester fiber is lowered and the heat resistance and hydrolysis resistance are deteriorated.

The intrinsic viscosity of the copolymerized polyester (measured in orthochlorophenol at 35 ° C.) is not particularly limited, but is preferably from 0.55 to 0.85 from the viewpoints of yarn production and fiber properties.
In order to copolymerize the organic sulfonic acid metal salt, as in the case of copolymerizing the above-described diol compound and / or epoxy compound formula, any stage until the synthesis of the polyester is completed, for example, the first stage It may be added at any stage such as before the start of the reaction, during the reaction, after the completion of the reaction, or during the second stage reaction, and the polycondensation reaction may be completed after the addition.

  In producing the copolyester of the present invention, a conventionally known hindered phenol antioxidant, hindered amine light stabilizer or ultraviolet absorber (benzotriazole, benzotriazine, benzophenone, etc.) is added as a stabilizer. This not only has the effect of suppressing thermal degradation, oxidation degradation, photodegradation, etc. during the use of the side chain copolymerized polyester fiber, but also has the effect of inhibiting the decrease in the intrinsic viscosity of the polymer during melt spinning. It is rather preferable.

  In order to make the copolymerized polyester obtained in this way into fibers, it is not necessary to adopt a special method, and a normal polyester fiber spinning method is arbitrarily applied. For example, it is manufactured by a method in which a copolymerized polyester is melted, discharged from a spinneret and wound up, and then subjected to stretching or heat treatment as necessary. The spun fiber may be a solid fiber having no hollow part, a hollow fiber having a hollow part, or an irregular shape. Further, the outer shape and the shape of the hollow part in the cross section of the spun fiber may be circular or irregular.

  Specific spinning methods include melt spinning at a speed of 500 to 2500 m / min, drawing and heat treatment, melt spinning at a speed of 2500 to 5000 m / min, and drawing and false twisting simultaneously and sequentially. A spinning method such as a method in which melt spinning is performed at a high speed of 5000 / min or more and the drawing step is omitted depending on the application may be arbitrarily adopted.

The copolymerized polyester fiber in the method of the present invention may contain optional additives such as an anti-coloring agent, a heat-resistant agent, a flame retardant, a matting agent, a coloring agent, and inorganic fine particles as necessary.
The copolyester fiber thus obtained may be either a long fiber or a short fiber, and the total fineness and single yarn fineness can be arbitrarily selected.

  According to the method of the present invention, the copolyester fiber is treated with a water-soluble metal salt of a metal selected from nickel, manganese and barium. At that time, the water-soluble metal salt is preferably used in the form of an aqueous solution such as an aqueous solution. At least a part of the metal of the organic sulfonic acid metal salt (alkaline metal other than alkali metal or barium) copolymerized with the polyester constituting the copolymer polyester fiber by this treatment is selected from nickel, manganese and barium. It is replaced with a metal and the effect of improving light resistance is exhibited.

As the water-soluble metal salt, any metal salt that is water-soluble at the treatment temperature can be used. Preferred examples include inorganic salts and organic carboxylates of nickel, manganese and barium. Specific examples include nickel sulfate, nickel chloride, nickel sulfamate [Ni (NH ₂ SO ₃ ) ₂ ], manganese sulfate, manganese chloride, barium chloride, barium acetate and the like. These water-soluble metal salts may be used alone or in combination of two or more.

  As a treatment condition for replacing the metal of the organic sulfonic acid metal salt copolymerized in the polymer constituting the copolymerized polyester fiber with a metal selected from nickel, manganese and barium by this treatment, the water-soluble metal salt concentration is Is preferably in the range of 0.1 g / L to 10 g / L, the processing temperature is not lower than the glass transition temperature of the copolyester fiber, is lower than 130 ° C., and the processing time is in the range of 30 minutes to 180 minutes.

  The amount of metal selected from nickel, manganese and barium contained in the copolymerized polyester fiber by such treatment is preferably in the range of 500 ppm to 30000 ppm based on the fiber weight. If the content of the metal selected from nickel, manganese and barium is too small, the effect of improving the light resistance will be insufficient. Conversely, if the content is too large, the light resistance will no longer show a significant improvement, and the physical properties such as fiber strength will be lost. There is a tendency to decrease. A more preferred content is in the range of 1000 ppm to 8000 ppm, still more preferably 2000 ppm to 6000 ppm.

  The form of the copolyester fiber at the time of performing the above treatment may be any of a yarn casserole shape, a cheese winding shape, a cotton shape, and a woven or knitted fabric. It is also possible to replace the metal while dyeing by dissolving the functional metal salt in the dye bath. Further, in the finishing step after dyeing, it can be replaced by treatment in a water bath containing the water-soluble metal salt. In addition, the pad steam method or the like can also be applied.

Copolymerized polyester fibers excellent in light resistance obtained by the method of the present invention may be used alone, but if necessary, natural fibers such as cotton and wool, regenerated fibers such as rayon and acetate, or the fibers of the present invention. It may be blended or woven with synthetic fibers other than copolymer polyester fibers.
Thus, the textile product using at least a part of the light-resistant copolymerized polyester fiber produced according to the present invention is extremely useful particularly in apparel applications such as the field of sportswear used in the outdoors and the field of midsummer clothing. .

The following can be mentioned as specific examples of the fiber product suitable for use of the fiber obtained by the method of the present invention.
(1) Clothing use Shirts, blouses, pants, blouses, coats, Japanese clothing, etc. for fashion use, underwear, bras, girdles, body fur, camisole, shorts, pantyhose, stockings, socks, high socks, short for use as inner legs Game shirts and game pants for sports use such as socks (tennis, basketball, table tennis, volleyball, track, golf, soccer, rugby, etc.), sweat suits, windbreakers, athletic wear, training wear, shorts, swimwear, swimming pool Sidewear, underwear, tights, spats, leotards, leg clothing, wet suits, dry suits, nightclothes, uniforms, school uniforms, hats, shawls and other clothing accessories, Lining, clothing materials such as cups and pads, sports shoes, etc. (2) Interior / Bedding Applications Curtains (draping curtains, lace curtains, shower curtains, roll curtains, blinds, etc.), carpets, tablecloths, chairs, partitions, wallpaper, Bedding (bed comforters, mattresses, futon bedding, futon stuffing, blankets, blanket bedding, towels, sheets, etc.), slippers, mats, etc. (3) Car interior materials Car seats, car mats, ceiling materials, trims, etc. (4) Industrial materials use Tents (for leisure, events, etc.)
Among these uses, it is particularly preferably used in the field of sportswear, midsummer wear, and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited by these. In addition, unless otherwise indicated, the part and% in each example show a weight part and weight%, respectively. In addition, the measurement of the moisture absorption rate in an Example was implemented by the following method, and ultraviolet irradiation was based on the following method. Further, the metal in the copolyester fiber was quantified by ICP emission spectroscopy.

<Hygroscopic rate>
The sample was conditioned for 24 hours in a constant temperature and humidity chamber adjusted to 35 ° C. and 95% RH, and the moisture absorption rate was determined from the weight of the absolutely dry sample and the weight of the conditioned sample according to the following equation.

<UV irradiation>
Using an ultraviolet fade meter manufactured by Suga Test Instruments Co., Ltd., set the knitted fabric sample in a large holder, and set the temperature of the black panel to 63 ° C and the temperature of the test chamber wet bulb to 33 ° C for 20 hours using an ultraviolet carbon arc. UV irradiation was applied.

<Moisture absorption retention>
A knitted fabric described later was used as a sample to perform a quantitative analysis of the metal, to perform predetermined ultraviolet irradiation, and to measure the moisture absorption rate before and after the ultraviolet irradiation. The UV-irradiated sample was thoroughly washed with water and then subjected to moisture absorption measurement. The retention rate was calculated by the following equation using the measured moisture absorption values before and after UV irradiation.

[Reference Example 1]
<Manufacture of copolymerized polyester polymer, fiber and knitted fabric (knitted fabric 1)>
100 parts of dimethyl terephthalate, 4 parts of sodium 3,5-dicarbomethoxybenzenesulfonate (2.6 mol% with respect to dimethyl terephthalate), 60 parts of ethylene glycol, 0.06 part of calcium acetate monohydrate (terephthalic acid) 0.066 mol% with respect to dimethyl), 0.009 part of cobalt acetate tetrahydrate as a color adjuster (0.007 mol% with respect to dimethyl terephthalate) and sodium acetate trihydrate as an ether by-product inhibitor 0 .11 parts (0.16 mol% with respect to dimethyl terephthalate) was charged into a transesterification can and heated up from 140 ° C to 220 ° C over 4 hours in a nitrogen gas atmosphere to distill off the methanol produced. The transesterification reaction was carried out. After completion of the transesterification reaction, 0.058 part of trimethyl phosphate (0.080 mol% based on dimethyl terephthalate) was added as a stabilizer. Then, 10 minutes later, 0.04 part of antimony trioxide (0.027 mol% with respect to dimethyl terephthalate) was added, and the temperature was raised to 240 ° C. while expelling excess ethylene glycol.

  After adding 20 parts of polyoxyethylene glycol methyl 1,2-dihydroxypropyl ether having an average molecular weight of 3000 (m = 66) (16% with respect to the copolymerized polyester) to the polymerization can, 760 Torr to 1 Torr over 1 hour The pressure was reduced to 240 ° C. and 280 ° C. over 1 hour 30 minutes. Under reduced pressure of 1 Torr or less, 0.8 parts of “Irganox 1010” (manufactured by Ciba Specialty Chemicals, registered commercial method) was added as an antioxidant at the time of polymerization for 2 hours at a polymerization temperature of 280 ° C. Polymerized for 30 minutes. The obtained polymer was chipped according to a conventional method.

  This chip was dried according to a conventional method, and then melt-spun at 285 ° C. using a spinneret having 24 circular spinning holes having a hole diameter of 0.3 mm. Next, the obtained undrawn yarn was drawn and heat-treated using a heating roller at 84 ° C. and a plate heater at 180 ° C. at a draw ratio such that the elongation of the drawn yarn finally obtained was 30%, and then 84 dtex. A / 24 filament drawn yarn was obtained. The obtained drawn yarn was knitted in accordance with a conventional method, smelted and preset to prepare a knitted fabric (hereinafter referred to as “knitted fabric 1”).

[Reference Example 2]
<Manufacture of copolymerized polyester polymer, fiber and knitted fabric (knitted fabric 2)>
4 parts of sodium 3,5-dicarbomethoxybenzenesulfonate used as a metal salt of organic sulfonate in Reference Example 1 (2.6 mol% with respect to dimethyl terephthalate) and sodium acetate 3 used as an ether by-product inhibitor A knitted fabric was produced in the same manner as in Reference Example 1 except that 0.11 part of a water salt (0.16 mol% with respect to dimethyl terephthalate) was not used (this is referred to as “knitted fabric 2”).

[Example 1]
After refining and presetting the “knitted fabric 1” produced in Reference Example 1 according to a conventional method, boiling conditions were obtained in an aqueous solution of nickel (II) sulfate hexahydrate 1 g / L and a bath ratio of 1/100. Processed for 1 hour below. The treated fabric was thoroughly washed with water and then air-dried. The obtained fabric was subjected to a metal quantitative analysis and subjected to predetermined ultraviolet irradiation, and the moisture absorption rate before and after the ultraviolet irradiation was measured. The sample subjected to ultraviolet irradiation was thoroughly washed with water and then subjected to moisture absorption measurement. The results were as shown in Table 1 below.

[Comparative Example 1]
Except not using the nickel (II) sulfate hexahydrate used as the water-soluble metal salt in Example 1, treatment under boiling conditions, washing with water, and air drying were performed in the same manner as in Example 1. The measurement results and retention rates of moisture absorption before and after ultraviolet irradiation were as shown in Table 1 below.

[Examples 2-3]
The same procedure as in Example 1 was conducted except that the amount of nickel sulfate (II) hexahydrate used as the water-soluble metal salt in Example 1 was changed to the concentration shown in Table 1. The results were as shown in Table 1 below.

[Examples 4 to 6]
Except for using nickel (II) sulfate pentahydrate instead of nickel sulfate (II) hexahydrate used as the water-soluble metal salt in Example 1, and using the same amount as described in Table 1. The same operation as in Example 1 was performed. The results were as shown in Table 1 below.

[Examples 7 to 9]
Similar to Example 1 except that barium acetate anhydrous salt was used instead of the nickel (II) sulfate hexahydrate used as the water-soluble metal salt in Example 1 and the amount used was set to the concentration shown in Table 1. Went to. The results were as shown in Table 1 below.

[Comparative Examples 2 to 4]
After refining and presetting the knitted fabric 2 produced in Reference Example 2 according to a conventional method, it boils at a bath ratio of 1/100 in an aqueous solution in which the water-soluble metal salts listed in Table 1 are dissolved in the concentrations listed in Table 1. Treated under conditions for 1 hour. Thereafter, the same procedure as in Example 1 was performed. The results were as shown in Table 1 below.

[Comparative Example 5]
The treatment was performed under boiling conditions in the same manner as in Comparative Examples 2 to 4 except that the water-soluble metal salt used as the water-soluble metal salt in Comparative Examples 2 to 4 was not used. Table 1 shows the measurement results and retention rates of moisture absorption before and after UV irradiation.

  The copolymerized polyester fiber produced by the method of the present invention is excellent in hygroscopicity, water absorption and quick-drying properties, and has extremely superior thermal conductivity and moisture permeability that have never existed before, especially natural fibers such as cotton and linen. It can express a refreshing and cool feeling. In addition, there is an advantage that there is little deterioration in properties such as hygroscopicity, water absorption, thermal conductivity, and moisture permeability due to sun exposure. Therefore, the fiber structure such as a woven or knitted fabric or nonwoven fabric containing the copolymerized polyester fiber according to the present invention and the fiber product are extremely useful particularly in apparel applications such as the field of sportswear used in the outdoors and the field of midsummer wear.

Claims (4)

A polyester having polyalkylene terephthalate as a main structural unit, wherein a polyether component is copolymerized in the side chain of the polyester, and an organic sulfonic acid metal salt represented by the following general formula (1) is contained in the polyester. A method for producing a copolymerized polyester fiber excellent in light resistance, characterized by treating a fiber comprising a copolymerized polyester with a water-soluble metal salt of a metal selected from nickel, manganese and barium.

2. The light resistance according to claim 1, wherein the polyether component copolymerized in the side chain is a diol compound represented by the following general formula (2) and / or an epoxy compound represented by the following general formula (3). A method for producing a copolyester fiber having excellent properties.

  The amount of copolymerization of the polyether component copolymerized in the side chain is 0.5 to 50% by weight with respect to the copolymerized polyester, and has excellent light resistance according to claim 1 or 2. A method for producing a copolyester fiber.   The amount of copolymerization of the organic sulfonic acid metal salt is 0.5 to 20 mol% with respect to the bifunctional carboxylic acid component constituting the copolymerized polyester. The manufacturing method of the copolyester fiber excellent in light resistance as described in a term.