JP2008222963A - Copolymerized polyester, copolymerized polyester fiber and fiber product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new copolymerized polyester being improved in both of the level of antifouling property and durability, also giving a fiber hardly lowering in these functionalities by the exposure to sunlight, and to provide a fiber and a fiber product formed of the copolymerized polyester. <P>SOLUTION: The copolymerized polyester having an alkylene terephthlate as a main constituent unit, in which a polyether component is copolymerized to its end, and further to which at least one kind of metal salt of a specified organic sulfonic acid selected from the group consisting of a nickel salt, a manganese salt and a barium salt is copolymerized, forms a product, such as a fiber, superior in antifouling property and durability. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a copolyester and fibers and fiber products comprising the copolyester. More specifically, a novel copolyester that gives a molded product (fiber, etc.) that is particularly excellent in antifouling property, in particular, recontamination prevention during washing, and that has little decrease in antifouling property due to sun exposure, The present invention relates to a fiber and a fiber product having improved antifouling property comprising a copolyester.

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 and difficult to remove than hydrophilic fibers such as cotton, and the stains are likely to re-adhere during washing (re-contamination). is there.
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 (Patent Document 2 below), a method by low-temperature plasma treatment of a gas containing oxygen (see Non-Patent Document 1 below), and the like are known.

  However, these methods are all proposed as finish processing (fiber surface processing) of polyester fiber products, and the operation is complicated, special equipment is required, processing reproducibility is poor, etc. There are problems in terms of processing, and clothing such as underwear and lab coats that are frequently washed has a problem that the initial effect gradually disappears as the number of washing 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. It is an object of the present invention to provide a novel copolyester, its fiber and fiber product, which are remarkably improved and have little antifouling property and decrease in 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, the polyester obtained by copolymerizing one end-capped polyethylene glycol constituting the antifouling polyester is further copolymerized with a metal salt selected from nickel, manganese and barium of a specific organic sulfonic acid, thereby finally It has been found that the level of antifouling property and durability of the resulting copolyester are improved, and that the functional degradation is significantly prevented 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 novel polyester copolymer, its fiber and fiber product are provided.

〔２〕末端に共重合されているポリエーテル成分が、下記一般式（２）で表わされる片末端封鎖ポリオキシアルキレングリコールであることを特徴とする上記〔１〕の共重合ポリエステル。

〔３〕末端に共重合されるポリエーテル成分の共重合量が、共重合ポリエステルに対して０．５〜１０重量％であることを特徴とする上記〔１〕又は〔２〕に記載の共重合ポリエステル。
〔４〕有機スルホン酸金属塩の共重合量が、末端共重合型ポリエステルを構成する二官能性カルボン酸成分に対して０．２〜５モルであることを特徴とする上記〔１〕から〔３〕のいずれかに記載の共重合ポリエステル。
〔５〕ポリエステルの分子鎖中に有機スルホン酸金属塩がランダムに共重合されている上記〔１〕から〔４〕のいずれかに記載の共重合ポリエステル。
〔６〕上記〔１〕から〔５〕のいずれかに記載の共重合ポリエステルからなることを特徴とする防汚性、耐久性の改善された共重合ポリエステル繊維。
〔７〕上記〔６〕に記載の共重合ポリエステル繊維を少なくとも一部に含んでなる繊維製品。 [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 copolymerized polyester, wherein a salt is copolymerized.

[2] The copolyester according to [1] above, wherein the polyether component copolymerized at the terminal is a one-end blocked polyoxyalkylene glycol represented by the following general formula (2).

[3] The copolymer according to the above [1] or [2], wherein the copolymerization amount of the polyether component copolymerized at the terminal is 0.5 to 10% by weight with respect to the copolymerized polyester. Polymerized polyester.
[4] The copolymerization amount of the organic sulfonic acid metal salt is 0.2 to 5 mol with respect to the bifunctional carboxylic acid component constituting the terminal copolymerized polyester. [3] The copolyester according to any one of [3].
[5] The copolyester according to any one of [1] to [4] above, wherein an organic sulfonic acid metal salt is randomly copolymerized in the molecular chain of the polyester.
[6] A copolyester fiber having improved antifouling properties and durability, comprising the copolyester according to any one of [1] to [5].
[7] A fiber product comprising at least a part of the copolyester fiber according to [6].

  As described above, the copolyester of the present invention has significantly improved antifouling property and washing durability when made into fibers, etc., compared with the prior art, and particularly has excellent recontamination prevention property and darkening prevention property due to washing. Has improved. For this reason, the fiber made of the copolyester exhibits its advantages particularly when it is made into clothes having a high frequency of washing such as underwear, white coats such as food white coats, uniforms such as blouses for ladies, and linen materials such as table cloths. In addition, antifouling properties are maintained even after repeated washing, and blackening due to washing does not occur. Therefore, the fiber comprising the copolyester of the present invention is particularly useful in the field of linen supply such as rental uniforms.

Furthermore, the fiber made of the copolymerized polyester of the present invention has the advantage that the above-mentioned antifouling property and exposure to washing due to exposure to sunlight are significantly reduced. Therefore, fiber structures and textile products such as woven and knitted fabrics and nonwoven fabrics containing the copolymerized polyester fiber of the present invention are frequently washed and used in the sun, especially in outdoor sportswear fields and high-summer clothing fields. It is also extremely useful in apparel applications with a large amount of clothes.
Moreover, the same effect can be expected even in a molded product other than the fiber made of the copolymerized polyester of the present invention, for example, a molded product of a film, a tape, or other forms.

  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 substituted with another bifunctional carboxylic acid component and / or a part of the glycol component is the above-mentioned glycol or other diol component other than the main 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 that causes a condensation reaction.

  In the copolymerized polyester of the present invention, it is necessary that at least one end of the molecular chain of the polyester is copolymerized with a polyether component, in particular, one end-blocked oxyalkylene glycol represented by the following general formula (2). It is. 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).

  In the general formula (2), R1 represents a hydrocarbon group, 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 carbon. An alkylaryl group having 8 to 16 atoms is preferred. R2 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. N in the general formula (2) is a positive integer indicating the degree of polymerization, and is preferably in the range of 30 to 140.

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.

  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. X1 represents an ester-forming functional group, and X2 represents an ester-forming functional group that is the same as or different from X1, or represents a hydrogen atom, but is preferably an ester-forming functional group. These ester-forming functional groups may be any group that reacts with and bonds to the main chain or terminal of the polyester, and specific examples thereof include the following groups.

そして、上記一般式（１）におけるＭ１は、Ｎｉ（ニッケル）、Ｍｎ（マンガン）及びＢａ（バリウム）よりなる群から選ばれた少なくとも１種の金属である。

M1 in the general formula (1) is at least one metal selected from the group consisting of Ni (nickel), Mn (manganese), and Ba (barium).

  Preferable specific examples of the organic sulfonic acid metal salt represented by the general formula (1) include nickel 3,5-dicarbomethoxybenzene sulfonate, manganese 3,5-dicarbomethoxybenzene sulfonate, 3,5-di Carbomethoxybenzene barium sulfonate, nickel 3,5-dicarboxybenzenesulfonate, manganese 3,5-dicarboxybenzenesulfonate, barium 3,5-dicarboxybenzenesulfonate, 3,5-di (β-hydroxyethoxy) Carbonyl) nickel benzenesulfonate, manganese 3,5-di (β-hydroxyethoxycarbonyl) manganese sulfonate, barium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate, 2,6-dicarbomethoxynaphthalene 4-sulphonic acid nickel, 2,6-di Rubomethoxynaphthalene-4-sulfonic acid manganese, 2,6-dicarbomethoxynaphthalene-4-barium sulfonic acid, nickel 2,6-dicarboxynaphthalene-4-sulfonic acid, 2,6-dicarbomethoxynaphthalene-1- Nickel sulfonate, nickel 2,6-dicarbomethoxynaphthalene-3-sulfonate, nickel 2,6-dicarbomethoxynaphthalene-4,8-disulfonate, 2,6-dicarboxynaphthalene-4,8-disulfonic acid Examples thereof include nickel and nickel 2,5-bis (hydroethoxy) benzenesulfonate. These organic sulfonic acid metal salts may be used alone or in combination of two or more.

  The copolymerization amount of the organic sulfonic acid metal salt is preferably in the range of 0.2 to 5 mol%, more preferably 0.5 to 4.5, based on the total amount of the bifunctional carboxylic acid component constituting the copolymer polyester. It is the range of mol%, More preferably, it is the range of 1.0-3.5 mol%. If the copolymerization amount of the organic sulfonic acid metal salt is too small, the antifouling property of the resulting fiber and the effect of improving the washing durability and light resistance 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 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 the copolyester of the present invention, conventionally known hindered phenol antioxidants, hindered amine light stabilizers and ultraviolet 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 preferred molecular weight of the copolyester of the present invention varies depending on its use, but when used for fiber production, the intrinsic viscosity measured at 35 ° C. in O-chlorophenol is preferably in the range of 0.55 to 0.85. It is.

  In addition to the stabilizer, the copolymerized polyester of the present invention contains optional additives as necessary, such as anti-coloring agents, heat-resistant agents, flame retardants, matting agents, coloring agents, inorganic fine particles and the like. There is no problem.

  In order to make the copolyester thus obtained into a fiber, it is not necessary to adopt a special method, and a normal method for producing a polyester fiber 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.

  As a spinning method, a method of melt spinning at a speed of 500 to 2500 m / min and drawing and heat treatment, a method of spinning at a speed of 2500 to 5000 m / min and performing drawing and false twisting simultaneously or sequentially 5000 / A method of spinning at a high speed of more than a minute and omitting the stretching step can be arbitrarily adopted 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.

Furthermore, the copolymerized polyester fiber of the present invention is used for blending, interweaving and the like with natural fibers such as cotton and wool, regenerated fibers such as rayon and acetate, and synthetic fibers other than the polyester of the present invention, as necessary.
Specific examples of the fiber product comprising at least a part of the copolyester fiber of the present invention 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 clothes, hats, shawls and other clothing accessories, linings, cups, pads and other clothing materials, sports shoes, etc. (2) Interior / bedding applications Curtains (draping curtains, lace curtains, shower curtains, roll curtains, blinds, etc.) , Carpets, tablecloths, upholstered chairs, partitions, wallpaper, bedding (comforters, mattresses, futon lining, blankets, blankets, blankets, towels, sheets, etc.), slippers, mats, etc. (3) Automobiles Interior material use Car seat, car mat, ceiling material, trim, etc. (4) Industrial material use Tents (for leisure, for events, etc.)

Among the above-mentioned uses, it is especially effective when used in clothes such as underwear, food lab coats, uniforms such as blouse for ladies, and linen materials such as table cloths. Linen such as rental uniforms It is particularly useful in the supply field.
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.
Although the fiber has been described in detail above, the same effect can be expected when the copolymerized polyester of the present invention is formed into a film, tape, or other molded body.

  Hereinafter, the present invention will be specifically described 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. The metal content in the copolymerized polyester fiber was quantified by ICP emission spectroscopic analysis. Furthermore, antifouling treatment, antifouling property evaluation and ultraviolet irradiation were performed by 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.

上記数式中、△Ｅ＊は防汚性を示し、この値が小さいほど防汚性に優れることを示す。
Ｌ１、ａ１、ｂ１はそれぞれ汚染処理前の試料のＬ＊、ａ＊、ｂ＊値を示し、Ｌ２、ａ２、ｂ２はそれぞれ洗濯後の試料のＬ＊、ａ＊、ｂ＊値を示す。 <Anti-fouling evaluation>
Using a Minolta Color Difference Meter CR-200 (Minolta Camera Sales Co., Ltd.), measure the LIE, C *, and L * values of the CIE color system of the sample. Asked.

In the above formula, ΔE * indicates antifouling property, and the smaller this value, the better the antifouling property.
L1, a1, and b1 respectively indicate L *, a *, and b * values of the sample before the contamination treatment, and L2, a2, and b2 indicate L *, a *, and b * values of the sample after washing, respectively.

<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 black carbon panel temperature to 63 ° C and the test bath wet bulb temperature to 33 ° C for 20 hours. Ultraviolet irradiation by arc was performed.

[Example 1]
100 parts of dimethyl terephthalate, 4 parts of nickel 3,5-dicarbomethoxybenzenesulfonate (1.3 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) and 0.009 part of cobalt acetate tetrahydrate (0.007 mol% with respect to dimethyl terephthalate) as a color adjuster were charged in a transesterification can and placed in a nitrogen gas atmosphere for 4 hours. The ester exchange reaction was carried out while distilling out the methanol produced by heating from 140 ° C. to 220 ° C. over the system. 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), the pressure was reduced from 760 Torr to 1 Torr over 1 hour, At the same time, the temperature was raised from 240 ° C. to 280 ° C. over 1 hour 30 minutes. When further polymerizing at a polymerization temperature of 280 ° C. for 2 hours under a reduced pressure of 1 Torr or less, 0.8 part of Irganox 1010 (manufactured by Ciba Specialty Chemicals) was added in vacuo as an antioxidant, and then polymerized for another 30 minutes. The obtained polymer was chipped according to a conventional method. The intrinsic viscosity of this polymer was 0.65.

  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 using the obtained drawn yarn, and refining and heat treatment were performed by a conventional method.

  The plain woven fabric thus produced was used as a test sample for quantitative metal analysis. Moreover, predetermined ultraviolet irradiation was given using a part of this plain fabric sample. The sample with “ultraviolet irradiation” and the sample without “ultraviolet irradiation” (control sample) not subjected to the ultraviolet irradiation were subjected to contamination treatment to evaluate the antifouling property. The results were as shown in Table 2.

[Comparative Example 1]
Transesterification reaction, polymerization reaction, chip formation, chip drying, in the same manner as in Example 1 except that 4 parts of nickel 3,5-dicarbomethoxybenzenesulfonate used as the organic sulfonic acid metal salt in Example 1 was not used. Spinning, drawing heat treatment, weaving, refining, and heat treatment were performed. The measurement results of the obtained plain woven fabric samples were as shown in Table 2.

[Examples 2 to 5]
The same procedure as in Example 1 was performed except that the amount of nickel 3,5-dicarbomethoxybenzenesulfonate used as the organic sulfonic acid metal salt in Example 1 was changed to the amount shown in Table 2. The results were as shown in Table 2.

[Examples 6 to 9]
Instead of using 4 parts of nickel 3,5-dicarbomethoxybenzenesulfonate used as the organic sulfonic acid metal salt in Example 1, manganese 3,5-dicarbomethoxybenzenesulfonate was used in the amount described in Table 2. The same operation as in Example 1 was performed. The results were as shown in Table 2.

[Examples 10 to 13]
Instead of using 4 parts of nickel 3,5-dicarbomethoxybenzenesulfonate used as the organic sulfonate metal salt in Example 1, barium 3,5-dicarbomethoxybenzenesulfonate was used in the amount shown in Table 2. The same operation as in Example 1 was performed. The results were as shown in Table 2.

[Comparative Example 2]
Instead of 4 parts of nickel 3,5-dicarbomethoxybenzenesulfonate used as the organic sulfonate metal salt in Example 1, 4 parts of sodium 3,5-dicarbomethoxybenzenesulfonate (2 parts per 2 parts of dimethyl terephthalate) .6 mol%) and 0.11 part of sodium acetate trihydrate (0.16 mol% based on dimethyl terephthalate) as an ether by-product inhibitor was used in the same manner as in Example 1 except that the amounts shown in Table 2 were used. went. The results were as shown in Table 2.

  Since the copolyester of the present invention has the above-mentioned properties, the fiber made of the copolyester has improved antifouling properties and washing durability compared to conventional ones, and is particularly resistant to recontamination by washing. As a result, the anti-darkening property will be greatly improved.For example, when clothes are used for clothes such as underwear, food lab coats, uniforms such as blouse for ladies, linen materials such as table cloths, and other textile products. The advantage is exhibited especially, and even if washing is repeated, antifouling property is maintained and blackening due to washing does not occur. For this reason, the copolyester fiber of the present invention is particularly useful in the field of linen supply such as rental uniforms. Further, the fiber has an advantage that the above-mentioned antifouling property and its washing durability due to sun exposure are remarkably reduced.

Therefore, textile structures and textile products such as woven and knitted fabrics and nonwoven fabrics containing the copolymerized polyester fiber of the present invention have a high frequency of washing, particularly in outdoor sportswear and high-summer wear fields, and are opportunities to be sun-dried. It is also extremely useful in apparel applications with a large amount of clothes.
In addition to fibers, the copolymerized polyester of the present invention is also useful in fields such as films and tapes that require the same properties and functions as described above.

Claims (7)

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 copolyester characterized by being polymerized.

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

  The copolymerized polyester according to claim 1 or 2, wherein a copolymerization amount of the polyether component copolymerized at the terminal is 0.5 to 10% by weight with respect to the copolymerized polyester.   The copolymerization amount of the organic sulfonic acid metal salt is 0.2 to 5 mol with respect to the bifunctional carboxylic acid component constituting the terminal copolymerization type polyester. 2. Copolyester according to item 1.   The copolymer polyester according to any one of claims 1 to 4, wherein an organic sulfonic acid metal salt is randomly copolymerized in a molecular chain of the polyester.   A copolyester fiber having improved antifouling property and durability, comprising the copolyester according to any one of claims 1 to 5.   A fiber product comprising the copolymerized polyester fiber according to claim 6 at least in part.