JP2008240200A - Method for producing copolyester fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing copolyester fibers which have more improved staining resistance and water resistance, especially largely more improved restaining resistance and blackening resistance, than those of the same kind of conventional fibers. <P>SOLUTION: This method for producing the copolyester fibers is characterized by treating fibers comprising a copolyester containing a polyalkylene terephthalate as a main constituting component and copolymerized with a polyether component at the terminals of the polyester and further copolymerized with a specific metal organic sulfonate such as sodium 3,5-dicarbomethoxybenzenesulfonate, with a water-soluble salt of a metal selected from nickel, manganese and barium to 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. More particularly, the present invention relates to a method for industrially producing a copolyester fiber that is particularly excellent in antifouling property, in particular, recontamination prevention during washing, and that has little decrease in antifouling property due to exposure to sunlight. is there.

  Polyester fibers have been used in many fields in the past because they have many excellent properties such as good dimensional stability, strength, and resistance to wrinkles. However, since polyester is hydrophobic, oily stains are more likely to adhere compared to hydrophilic fibers such as cotton, and the attached stains are difficult to remove, and the stains are more likely to reattach during washing ( (Re-contamination).

This re-contamination property has always been a problem since the practical use of polyester fibers, and many methods have been proposed to solve this problem.
For example, a method of immersing a polyester molded product in a solution or dispersion comprising a copolymer of polyethylene glycol and a polyester resin (see Patent Document 1 below), a hydrophilic vinyl compound such as polyethylene glycol dimethacrylate, or a pad or spray. A method of post-steaming heat treatment (see Patent Document 2 below), a method using a low-temperature plasma treatment of a gas containing oxygen (see Non-Patent Document 1 below), and the like are known.

  However, these methods have problems in processing such as complicated operation, special equipment, poor reproducibility of processing, and clothes with a high frequency of washing such as underwear and lab coats. Has a problem that the initial effect gradually disappears as the number of washings is repeated. In addition, among the above conventional methods, in the method using a polyethylene glycol compound as a hydrophilizing agent, the polyethylene glycol compound adhering to the fiber surface is easily decomposed and dropped by ultraviolet rays contained in sunlight, and the antifouling property is lowered. There is a tendency, and the use in apparel that is exposed to sunlight, such as the field of sportswear used outdoors and the field of midsummer clothing, is remarkably restricted.

  On the other hand, as an antifouling polyester fiber by polymer modification, an antifouling polyester fiber obtained by copolymerizing one end-capped polyethylene glycol at the end of a polyester main chain has been proposed (see Patent Documents 3 to 6 below). According to this method, a specific fiber microstructure is formed in the fiber formation process by the action of polyethylene glycol copolymerized at the terminal, and therefore, an excellent antifouling initial performance which is not conventionally obtained can be obtained. Furthermore, since the polyethylene glycol chain is molecularly bonded to the polyester main chain by a strong covalent bond, its washing durability is remarkably improved. However, since such an antifouling polyester fiber also uses a polyethylene glycol compound as a hydrophilic component, it has a significant advantage over the fiber surface processing method described above, but in applications where it is exposed to sunlight for a long time. In some cases, deterioration of the antifouling property becomes a problem, and further improvement has been desired.

Japanese Patent Publication No. 47-2512 Japanese Patent Publication No.51-2559 JP-A-62-90312 JP-A-63-35824 JP 63-35825 A JP-A-63-50524 “Polymer” August 1978, pp. 904-912

  The present invention has been made in view of the above-described background art, and its object is to significantly improve the antifouling property and its washing durability as compared with the conventional ones. An object of the present invention is to provide a method capable of producing a copolyester fiber which is remarkably improved and has little deterioration in antifouling property and washing durability due to sun exposure.

  In order to achieve the above-mentioned object, the present inventors made various studies by paying attention to the antifouling polyester obtained by copolymerizing the above-mentioned one-end-capped polyethylene glycol at the terminal of the polyester main chain. As a result, by copolymerizing the single-end-capped polyethylene glycol constituting the antifouling polyester and further treating the copolymerized polyester fiber copolymerized with a specific organic sulfonic acid metal salt with a specific water-soluble metal salt The present inventors have found that the level of antifouling property of the fiber finally obtained and its durability are improved, and that the functionalities are not significantly reduced by exposure to sunlight, and the above-mentioned problems can be achieved. The present invention has been completed as a result of further research based on these findings.

  Thus, according to the present invention, the following method for producing a polyester copolymer fiber is provided.

[1] A polyester having polyalkylene terephthalate as a main structural unit, wherein a polyether component is copolymerized at the terminal of the polyester, and an organic sulfonic acid metal represented by the following general formula (1) in the polyester A process for producing a copolyester fiber, characterized in that a fiber comprising a copolyester having a copolymerized salt is treated with a water-soluble metal salt of a metal selected from nickel, manganese and barium.

[2] The copolyester of [1] above, wherein the polyether component copolymerized at the end of the copolyester is a one-end-capped polyoxyalkylene glycol represented by the following general formula (2) A method for producing fibers.

[3] The above [1] or [2], wherein the polyether component copolymerized at the terminal of the copolymerized polyester is 0.5 to 10% by weight based on the copolymerized polyester. ] The manufacturing method of the copolyester fiber of description.

[4] The copolymerization amount of the organic sulfonic acid metal salt at the terminal of the copolymerized polyester is 0.1 to 20 mol with respect to the bifunctional carboxylic acid component constituting the terminal copolymerized polyester. Copolyester in any one of said [1]-[3].

  According to the production method of the present invention as described above, the antifouling property and the washing durability when made into fibers or the like are significantly improved as compared with the prior art. A significantly improved copolyester fiber is obtained. Thus, the copolyester fiber according to the present invention is particularly suitable when it is made into a textile product with a high frequency of washing, such as underwear, lab coats for food handling lab coats, uniforms such as blouse for ladies, and linen materials such as tablecloths. Advantages are exhibited, anti-staining properties are maintained even after repeated washing, and no darkening due to washing occurs. Therefore, the copolyester fiber according to the present invention is particularly useful in the field of linen supply such as rental uniforms.

  Further, the copolyester fiber according to the present invention has the advantage that the above-mentioned antifouling property and its washing durability decrease due to sun exposure are remarkably small. Accordingly, fiber structures and textile products such as woven and knitted fabrics and nonwoven fabrics containing the copolymerized polyester fibers are frequently washed and frequently sun-dried, particularly in the field of sportswear used in the outdoors and in the field of midsummer clothing. It is also extremely useful in clothing applications.

  The polyester referred to in the present invention is a polyester having terephthalic acid as a main difunctional carboxylic acid component and at least one alkylene glycol, for example, at least one selected from ethylene glycol, trimethylene glycol and tetramethylene glycol as a glycol component, That is, the main object is polyester (alkylene terephthalate-based polyester) having alkylene terephthalate as a main structural unit.

  In such a polyester, a part of the terephthalic acid component (for example, 20 mol% or less) is replaced with another bifunctional carboxylic acid component and / or a part of the glycol component other than the main glycol or other diol component. Polyester substituted with may be used.

  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. it can. These other diol compounds are preferably used in an amount of 20 mol% or less.

  Furthermore, polycarboxylic acids such as trimellitic acid and pyromellitic acid, polyols such as glycerin, trimethylolpropane, and pentaerythritol can be used as long as 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 to be condensed.

  In the present invention, as a polymer for fiber production, a polyether component, particularly a single-end-blocked oxyalkylene glycol represented by the following general formula (2) is copolymerized at at least one end of the molecular chain of the polyester. is necessary. As used herein, the term “one-end blocked” means that one end group of oxyalkylene glycol is blocked with a non-functional hydrocarbon group as is apparent from the following general formula (2).

上記一般式（２）中、Ｒ_１は炭化水素基を示し、通常、炭素原子数１〜４のアルキル基、炭素原子数６〜１２のシクロアルキル基、炭素原子数６〜１２のアリール基又は炭素原子数８〜１６のアルキルアリール基が好ましい。また、Ｒ_２はアルキレン基であり、通常、炭素原子数２〜４のアルキレン基が好ましい。好適なアルキレン基としてはエチレン基、プロピレン基、テトラメチレン基が例示される。また、上記ポリオキシアルキレングリコールは、分子中に２種以上のアルキレン基が混在してもよく、例えばエチレン基とプロピレン基、もしくはエチレン基とテトラメチレン基とを持ったランダム共重合体やブロック共重合体であってもよい。上記一般式（２）中のｍは重合度を示す正の整数であり、通常、３０〜１４０の範囲が好ましい。

In the general formula (2), R ₁ represents a hydrocarbon group, which is usually 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 is an alkylene group, and usually an alkylene group having 2 to 4 carbon atoms is preferred. Suitable alkylene groups include an ethylene group, a propylene group, and a tetramethylene group. The polyoxyalkylene glycol may contain two or more kinds of alkylene groups in the molecule. For example, a random copolymer or block copolymer having an ethylene group and a propylene group, or an ethylene group and a tetramethylene group. It may be a polymer. M in the said General formula (2) is a positive integer which shows a polymerization degree, and the range of 30-140 is preferable normally.

Preferable specific examples of such one-end-capped polyoxyalkylene glycol include polyoxyethylene glycol monomethyl ether, polyoxyethylene glycol monophenyl ether, polyoxyethylene glycol monooctyl phenyl ether, polyoxyethylene glycol monononyl phenyl ether, polyoxyethylene glycol Ethylene glycol monocetyl ether, polyoxypropylene glycol monomethyl ether, polyoxypropylene glycol monophenyl ether, polyoxypropylene glycol monooctyl phenyl ether, polyoxypropylene glycol monononyl phenyl ether, polyoxytetramethylene glycol monomethyl ether, polyoxyethylene Glycol / polyoxypropylene glycol Monomethyl ether polymer, monomethyl ether of polyoxyethylene glycol / polyoxytetramethylene glycol copolymer and the like. Of these, polyoxyethylene glycol derivatives are particularly preferred.
The above single-end-capped polyoxyalkylene glycol may be used alone or in combination of two or more.

  In order to copolymerize the one-end-capped polyoxyalkylene glycol to at least one terminal of the polyalkylene terephthalate-based polyester, any stage until the synthesis of the above-described polyester is completed, for example, before the start of the first stage reaction, During the reaction, after the completion of the reaction, one-end-capped polyoxyalkylene glycol 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 antifouling property and its washing durability will be insufficient, and conversely if too large, the remarkable effect of improving the antifouling property and its washing durability will not be seen. On the contrary, the degree of polymerization of the copolyester is lowered, and the problem that physical properties such as strength of the copolyester fiber finally obtained becomes insufficient becomes apparent. For this reason, the copolymerization amount of the one-end-capped polyoxyalkylene glycol in the present invention is preferably in the range of 0.5 to 10% by weight, and in the range of 2 to 7% by weight, based on the copolymer polyester to be produced. Is particularly preferred.

  In the present invention, it is further necessary that a specific organic sulfonic acid metal salt represented by the following general formula (1) is copolymerized with the copolymer polyester. That is, in the above-described copolymer polyester, the organic sulfonic acid metal salt is further copolymerized to improve the antifouling property of the fiber obtained from the finally obtained copolymer polyester and its washing durability, and exposure to sunlight outdoors. The special effect that the antifouling property and the fall of the washing durability accompanying this are suppressed is seen.

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。これらの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. These ester-forming functional groups may be any group that reacts and bonds to the main chain or terminal of the side-chain copolymerized polyester, and specific examples thereof include the following groups.

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

  Preferable specific examples of the organic sulfonic acid metal salt represented by the general formula (1) include sodium 3,5-dicarbomethoxybenzenesulfonate, potassium 3,5-dicarbomethoxybenzenesulfonate, 3,5-dicarboxylate. Lithium carbomethoxybenzenesulfonate, sodium 3,5-dicarboxybenzenesulfonate, potassium 3,5-dicarboxybenzenesulfonate, lithium 3,5-dicarboxybenzenesulfonate, 3,5-di (β-hydroxyethoxy) Carbonyl) sodium benzenesulfonate, potassium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate, lithium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate, 2,6-dicarbomethoxynaphthalene 4-sulphonic acid sodium rim, 2,6 -Potassium dicarbomethoxynaphthalene-4-sulfonate, lithium 2,6-dicarbomethoxynaphthalene-4-sulfonate, sodium 2,6-dicarboxynaphthalene-4-sulfonate, 2,6-dicarbomethoxysphthalene -1-sodium sulfonate, 2,6-dicarbomethoxynaphthalene-3-sodium sulfonate, 2,6-dicarbomethoxynaphthalene-4,8-sodium disulfonate, 2,6-dicarboxynaphthalene-4,8 Examples thereof include sodium disulfonate, sodium 2,5-bis (hydroethoxy) benzenesulfonate, α-sodium sulfosuccinic acid and the like. These organic sulfonic acid metal salts may be used alone or in combination of two or more.

Among these organic sulfonic acid metal salts, sodium 3,5-dicarbomethoxybenzenesulfonate is particularly preferable because it is easily available and has good handleability.
The copolymerization amount of the organic sulfonic acid metal salt is preferably in the range of 1.0 to 20 mol%, more preferably 1 to 15 mol% with respect to the total amount of the bifunctional carboxylic acid component constituting the copolymerized polyester. The range is more preferably 2 to 10 mol%. If the copolymerization amount of the organic sulfonic acid metal salt is too small, the antifouling property of the resulting fiber and its washing durability and light resistance are not sufficiently improved. 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 is lowered, and the heat resistance, hydrolysis resistance and the like are deteriorated.

The organic sulfonic acid metal salt is preferably randomly copolymerized in the polyester molecular chain (main chain) of the copolymerized polyester.
In order to copolymerize the organic sulfonic acid metal salt, in the same manner as in the case of copolymerization of one-end-capped polyoxyalkylene glycol, any stage until the synthesis of the polyester described above is completed, for example, the start of the first stage reaction It may be added at any stage such as before, during the reaction, after completion of the reaction, or during the second stage reaction, and the polycondensation reaction may be completed after the addition.

  In producing such a copolyester, conventionally known hindered phenol antioxidants, hindered amine light stabilizers and UV absorbers (benzotriazole, benzotriazine, benzophenone, etc.) are added as stabilizers. This not only has the effect of suppressing thermal degradation, oxidation degradation, photodegradation, etc. during use of the copolyester or its fibers, but also has the effect of inhibiting a decrease in the intrinsic viscosity of the polymer at the time of melting. Rather, it is preferable.

The suitable molecular weight of the copolymerized polyester used in the present invention is preferably in the range of 0.55 to 0.85 in terms of intrinsic viscosity measured at 35 ° C. in O-chlorophenol.
In addition to the stabilizer, the copolyester 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, if necessary. There is no problem.

  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, the copolymerized polyester is produced by melt spinning and winding, and then stretching or heat treatment as necessary. The spun fiber may be a solid fiber having no hollow part or a hollow fiber having a hollow part. Moreover, the outer shape and the shape of the hollow part in the cross section of the spun fiber may be circular or irregular (non-circular). Furthermore, a modified hollow fiber having a modified cross section and having one or a plurality of hollow portions may be used.

  Specific spinning methods include melt spinning at a speed of 500 to 2500 m / min and drawing and heat treatment, spinning at a speed of 2500 to 5000 m / min, and drawing or false twisting simultaneously or sequentially. A method of spinning at a high speed of 5000 / min or more and omitting the stretching step may be arbitrarily employed depending on the application.

The copolyester fiber thus obtained may be either a long fiber or a short fiber, and the single yarn fineness and the total fineness can be arbitrarily selected according to the application.
The copolyester fiber thus obtained may be either a long fiber or a short fiber, and their single yarn fineness and total 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 (alkali metal, alkaline earth metal excluding barium) copolymerized with the copolyester constituting the copolyester fiber by this treatment is made of nickel, manganese and barium. By replacing the selected metal, the effect of improving light resistance is exhibited.

As such a water-soluble metal salt, any nickel salt, manganese salt or barium salt which is water-soluble at the treatment temperature can be used. Preferred salts include inorganic salts or organic salts of nickel, manganese and barium. Carboxylic acid salts can be mentioned. Among these, specific examples of suitable salts 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.

  By this treatment, at least a part of the metal of the organic sulfonic acid metal salt copolymerized in the polymer constituting the copolymerized polyester fiber is replaced with a metal selected from nickel, manganese and barium. As treatment conditions for that, the water-soluble metal salt concentration ranges from 0.1 g / L to 10 g / L, the treatment temperature ranges from the glass transition temperature of the copolymerized polyester fiber to less than 130 ° C., and the treatment time ranges from 30 minutes to 30 minutes. It can be preferably carried out in the range of 180 minutes.

  The total amount of metal selected from nickel, manganese and barium contained (introduced) in the copolyester fiber by such treatment is preferably in the range of 500 ppm to 30000 ppm based on the fiber weight. If the content of these metals 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 be improved significantly. There is a tendency for the physical properties of to decrease. Among these, a more preferable content is in the range of 1000 ppm to 8000 ppm, 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.

  The copolymerized polyester fiber obtained by the method of the present invention has improved antifouling property and durability for washing, and in particular, improved anti-contamination and anti-darkening properties due to washing, so it can be used in various fields. However, specific examples of suitable fiber products comprising at least part of the fibers include the following.

(1) Clothing use Shirts, blouses, pants, blousons, 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.), suits, windbreakers, athletic wear, training wear, shorts, swimwear, swimming pool Sidewear, underwear, tights, spats, leotards, leg clothing, wet suits, dry suits, white coats such as food white coats, uniforms such as ladies' blouses, nightwear use, School uniforms, clothing accessories such as hats and shawls, 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 (bedclothes, mattresses, futon bedding, futons) Padding, blankets, blankets, towels, sheets, etc.), slippers, mats, etc.

(3) Automotive interior materials applications Car seats, car mats, ceiling materials, trims, etc.

(4) Industrial materials use Tents (for leisure, events, etc.)
Among the above-mentioned applications, this is especially true when it is made into clothes with a high frequency of washing, such as underwear, lab coats for food handling, blouse for ladies, linen materials such as table cloths, etc. It is particularly useful in the field of linen supply. Furthermore, it is extremely useful in clothing applications that are frequently washed and frequently sun-dried, such as the field of sportswear used outdoors and the field of midsummer clothing.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited by these. In addition, unless otherwise indicated, the part and% in an Example and a comparative example show a weight part and weight%, respectively. Further, the metal content in the copolymerized polyester fiber in the examples was quantified by ICP emission spectroscopic analysis, and the antifouling treatment, antifouling evaluation and ultraviolet irradiation were according to the following methods.

<Contamination treatment>
A 10 cm × 10 cm plain woven fabric sample is placed in a treatment pot containing a laundry re-contamination liquid having the composition shown in Table 1 below with a load cloth (100% cotton scouring cloth) so that the bath ratio is 1: 260. The mixture was stirred at 50 ° C. for 60 minutes.

  After lightly washing with water, the sample was sandwiched between filter papers to remove excess contaminants. Next, the contaminated sample was washed in a household washing machine using the standard amount of synthetic detergent for washing, and the washing operation specified in JIS L 0217 Attached Table 1 No. 103 was defined as one cycle (one time). Repeated. The washing temperature was 55 ° C., and the drying was performed by indoor natural drying.

  Subsequently, antifouling property and whiteness were evaluated by the following methods. In addition, antifouling property was computed by the following numerical formula based on the L *, a *, b * value of the processed sample. The recontamination prevention property is evaluated by a value after 25 washings, and the smaller the value, the better the recontamination prevention property.

<UV irradiation>
Using a UV auto fade meter manufactured by Suga Test Instruments Co., Ltd., place 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. UV irradiation was applied.

[Reference Example 1]
<Manufacture of copolyester polymer, fiber and woven fabric (woven fabric 1)>
100 parts of dimethyl terephthalate, 4 parts of sodium 3,5-dicarbomethoxybenzenesulfonate (2.6 mol% based on 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 5 parts of polyoxyethylene glycol monomethyl ether having an average molecular weight of 4000 (n = 90) to the polymerization can (4.6% with respect to the copolyester), from 760 Torr to 1 Torr over 1 hour The pressure was reduced, and the temperature was raised from 240 ° C. to 280 ° C. over 1 hour and 30 minutes. Under a reduced pressure of 1 Torr or less, 0.8 part of “Irganox 1010” (registered trademark, manufactured by Ciba Specialty Chemicals) 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%. A drawn yarn of decitex / 24 filament was obtained. A plain woven fabric was woven according to a conventional method using the obtained drawn yarn. This is designated as “woven fabric 1”.

[Reference Example 2]
<Manufacture of copolyester polymer, fiber and woven fabric (woven fabric 2)>
4 parts of sodium 3,5-dicarbomethoxybenzenesulfonate used as the organic sulfonic acid metal salt in Reference Example 1 (2.6 mol% based on dimethyl terephthalate) and sodium acetate 3 used as an ether by-product inhibitor A plain woven fabric was prepared in the same manner as in Reference Example 1 except that 0.11 part of the water salt (0.16 mol% with respect to dimethyl terephthalate) was not used. This is designated as “fabric 2”.

[Example 1]
After refining and heat-treating “woven fabric 1” prepared in Reference Example 1 according to a conventional method, the solution was boiled in an aqueous solution of nickel (II) sulfate hexahydrate 1 g / L and a bath ratio of 1/100. Treated for 1 hour. The treated fabric was thoroughly washed with water and then air-dried. The obtained fabric was subjected to metal quantitative analysis to quantify the metal content. Moreover, predetermined ultraviolet irradiation was given to a part of the “woven fabric 1” sample. The sample with “ultraviolet irradiation” and the sample without “ultraviolet irradiation” (control sample) not subjected to the ultraviolet irradiation were each subjected to contamination treatment to evaluate the antifouling property. The results are shown in Table 2.

[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 antifouling property was evaluated for the sample that was subjected to ultraviolet irradiation and the sample that was not subjected to ultraviolet irradiation. The results are shown in Table 2.

[Examples 2 to 3]
The same procedure as in Example 1 was carried out except that the amount of nickel sulfate (II) hexahydrate used as the water-soluble metal salt in Example 1 was adjusted to the concentrations shown in Table 2. The results are shown in Table 2.

[Examples 4 to 6]
Manganese (II) sulfate pentahydrate was used in place of the nickel (II) sulfate hexahydrate used as the water-soluble metal salt in Example 1, and the amount used was the concentration described in Table 2. The same operation as in Example 1 was performed. The results are shown in Table 2.

[Examples 7 to 9]
Similar to Example 1 except that barium acetate anhydrous salt was used in place of the nickel (II) sulfate hexahydrate used as the water-soluble metal salt in Example 1 and the amount used was set to the concentrations shown in Table 2. Went to. The results are shown in Table 2.

[Comparative Examples 2 to 4]
After refining and presetting the “woven fabric 2” prepared 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 2 are dissolved to the concentrations listed in Table 2. The treatment was performed for 1 hour under the conditions, and thereafter the same treatment as in Example 1 was performed. The results are shown in Table 2.

[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 in Comparative Examples 2 to 4 was not used. The antifouling property was evaluated for the case where ultraviolet irradiation was performed using such a treated sample and the case where ultraviolet irradiation was not performed. The results are shown in Table 2.

  The copolymerized polyester fiber obtained by the method of the present invention has improved antifouling property and durability for washing compared to fibers obtained by the conventional method, and in particular, improved anti-contamination and anti-darkening properties due to washing. It is especially effective when it is made into clothes such as underwear, white robes, ladies' uniforms such as blouse, table cloths, etc., and linen materials such as tablecloths. No darkening occurs. For this reason, the fiber obtained by the method of the present invention is particularly useful in the field of linen supply such as rental uniforms. In addition, the fiber is significantly less susceptible to the above-described antifouling properties and washing durability associated with sun exposure. Therefore, fiber structures and textile products such as woven and knitted fabrics and nonwoven fabrics containing the fibers are used in clothing applications that are frequently washed and frequently sun-dried, particularly in the field of sportswear and outdoor clothing for outdoor use. Is also extremely useful.

Claims (4)

Polyester having polyalkylene terephthalate as a main structural unit, a polyether component is copolymerized at the terminal of the polyester, and an organic sulfonic acid metal salt represented by the following general formula (1) is co-polymerized in the polyester. A method for producing a copolymerized polyester fiber, comprising treating a fiber comprising a polymerized copolymerized polyester with a water-soluble metal salt of a metal selected from nickel, manganese and barium.

2. The copolymer polyester according to claim 1, wherein the polyether component copolymerized at the terminal of the copolymer polyester is a one-end-capped polyoxyalkylene glycol represented by the following general formula (2).

  The copolymerization amount of the polyether component copolymerized at the terminal of the copolymerized polyester is 0.5 to 10% by weight with respect to the copolymerized polyester. A method for producing a copolyester fiber.   The amount of copolymerization of the organic sulfonic acid metal salt in the copolymerized polyester is 0.1 to 20 mol% with respect to the bifunctional carboxylic acid component constituting the terminal copolymerized polyester. The copolyester according to any one of claims 3 to 4.