JPH0518948B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to polyester fibers with excellent antistatic durability, and more specifically, the present invention relates to polyester fibers with excellent antistatic durability, and more specifically, polyester fibers containing a specific antistatic agent are coated with a specific polyester copolymer. This invention relates to polyester fibers that have good antistatic durability, friction durability, and entanglement durability. (Prior Art) Polyesters, particularly polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate, and polyesters based on these have various excellent properties and are therefore widely used in fibers and the like. However, since such polyester is easily charged with static electricity, it has the drawback of easily causing various troubles during spinning, processing, use, and the like. Conventionally, various methods have been proposed to solve this drawback. For example, an antistatic polyester composition in which an insoluble polyoxyalkylene glycol and an alkylsulfonic acid metal salt are blended into polyester is known from JP-A-53-149246. Further, for the purpose of improving the dispersibility of polyester fibers for paper making in water, it has been proposed in JP-A-58-208500 to attach a polyester polyole block copolymer to polyester fibers. Furthermore, in order to improve the dispersibility in water and packaging workability of polyester fibers for paper making, it is particularly desirable to attach polyester prepared by copolymerizing an ester-forming alkali metal sulfonic acid salt compound and polyethylene glycol to polyester fibers. 1986-
It is known from Publication No. 224899. (Problems to be Solved by the Invention) However, the fibers made from the polyester composition described in JP-A No. 53-149246,
There is a problem in that the antistatic durability is poor, and the antistatic properties deteriorate with repeated washing. Also, JP-A-58-208500 or JP-A-Sho.
When the polyester copolymer described in Publication No. 60-224899 is attached to polyester fibers, the water dispersibility (or packaging workability) of the fibers improves, but it is not expected that the antistatic durability will improve. Can not. An object of the present invention is to solve the problems of the above-mentioned conventional technology and to provide an antistatic polyester fiber that has excellent antistatic durability after repeated washing with water, and also has excellent frictional durability and entanglement durability. It is in. Polyester fibers with excellent friction durability and entanglement durability are resistant to tearing and have little fuzz when used as stuffing for nonwoven fabrics, sanitary materials, quilting wear, etc., making it possible to obtain excellent products. (Means for Solving the Problems) In order to achieve the above object, the present inventors have made intensive studies and found that a specific polyester copolymer is added to polyester fibers containing a specific antistatic agent. The present inventors have discovered that by adhering them, antistatic durability is significantly improved, and friction durability and entanglement durability are also improved. That is, the present invention provides the following general formula [In the formula, n represents an integer of 2 to 6. ] Polyester 100 mainly consisting of repeating units represented by
0.1 to 10 parts by weight of a polyoxyalkylene glycol substantially inert to the polyester and/or the following general formula RSO ₃ M [wherein R represents an alkyl group having 8 or more carbon atoms, M
indicates an alkali metal. ] A polyester fiber made of terephthalic acid and/or isophthalic acid, a low number alkylene glycol, and a polyalkylene glycol and/or its monoether 0.2 to 40 mol% of an ester-forming alkali metal sulfonic acid salt compound ( dicarboxylic acid component) and average molecular weight
Antistatic polyester fibers with a polyester copolymer copolymerized with 500 to 12,000 polyethylene glycol 20 to 90% by weight (based on the polymer produced), with 13 crimps/25 mm or more. It is an antistatic polyester fiber that is a short fiber with
Antistatic polyester fiber. The polyester that is the base material of the fiber of the present invention has terephthalic acid as the main acid component, and alkylene glycol components having 2 to 6 carbon atoms, such as ethylene glycol, trimethyl glycol, tetramethylene glycol, pentamethylene glycol, and hexamethylene glycol. The target is a polyester whose main glycol component is at least one type of glycol selected from the following. Such polyester may be produced by any method; for example, for polyethylene terephthalate,
Terephthalic acid is produced by directly esterifying terephthalic acid and ethylene glycol, by transesterifying a lower alkyl ester of terephthalic acid such as dimethyl terephthalate with ethylene glycol, or by reacting terephthalic acid and ethylene oxide. It is easily produced by producing a glycol ester of an acid and/or a low polymer thereof, and then heating the product under reduced pressure to carry out a polycondensation reaction until a desired degree of polymerization is achieved. Note that in this polyester, a part of the terephthalic acid component may be replaced with another difunctional carboxylic acid component. Examples of such carboxylic acids include isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, diphenylcarboxylic acid, diphenoxyethanedicarboxylic acid, β-oxyethoxybenzoic acid,
Difunctional aromatic carboxylic acids such as p-oxybenzoic acid, difunctional aliphatic carboxylic acids such as sebacic acid, adipic acid, and oxalic acid, difunctional resinous carboxylic acids such as 1,4-cyclohexanedicarboxylic acid, etc. I can give it to you. Further, a part of the above glycol component may be replaced with other glycol components, such as aliphatic and fatty acids such as cyclohexane-1,4-dimethanol, neopentyl glycol, bisphenol A, and bisphenol S. Examples include cyclic and aromatic diol compounds. The polyoxyalkylene glycol blended into the fiber of the present invention may be a single polyoxyalkylene glycol or a copolymer polyoxyalkylene glycol of two or more types, as long as it is substantially insoluble in polyester. The terminal may be an -OH group, or it may be blocked with an organic group that does not have ester-forming properties, and it may also have other ester-forming properties via an ester bond, ether bond, or carbonate bond. It may be bonded to an organic group. A specific example is molecular weight.
Polyoxyethylene glycol with a molecular weight of 4000 or more, polyoxypropylene glycol with a molecular weight of 1000 or more,
Polyoxytetramethylene glycol, molecular weight
1:1 copolymer of ethylene oxide and propylene oxide with a molecular weight of over 2000, trimethylolethylene oxide adduct with a molecular weight of over 4000, molecular weight
Examples include 3000 or more nonylphenol ethylene oxide adducts. Particularly preferred is molecular weight
10000-100000 polyoxyethylene glycol,
It is a random copolymer of ethylene oxide and propylene oxide with a molecular weight of 10,000 to 3,000 in a ratio of 1:3 to 3:1. The appropriate amount of polyoxyalkylene glycol is in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the polyester medium. When the amount is less than 0.1 part by weight, sufficient antistatic properties cannot be obtained even if an appropriate amount of an alkylsulfonic acid metal salt, which will be described later, is used in combination. In addition, when the amount is more than 10 parts by weight, the physical properties of the resulting composition, especially the thermal properties, are greatly reduced;
Moreover, considering the antistatic property, by using an appropriate amount of the alkyl sulfonic acid metal salt described below,
It is not necessary to use more than 10 parts by weight. Especially 0.5~5
Parts by weight ranges are preferred. The alkyl sulfonic acid metal salt blended into the fiber of the present invention is represented by the general formula RSO ₃ M. Here, M represents an alkali metal, usually sodium, potassium,
Lithium is preferred, particularly sodium. R
represents an alkyl group having 8 or more carbon atoms. In the case of an alkyl group having 7 or less carbon atoms, the compatibility with polyester is poor, and if this is used, the moldability, particularly the thread-spinning property, deteriorates. Moreover, the durability of the antistatic property of the obtained product also becomes poor. Usually, those in which R is an alkyl group having 8 to 20 carbon atoms are used, and mixtures thereof are often used. The amount of the alkyl sulfonic acid metal salt is:
0.5 to 100 parts by weight of base polyester
In the range of 10 parts by weight. When the amount is less than 0.5 part by weight, no effective antistatic effect can be obtained. In addition, using 0.5 parts by weight or more of alkyl sulfonic acid metal salt,
When used together with polyoxyalkylene glycol,
A synergistic effect is obtained, and a sufficient antistatic effect can be achieved with a small amount of polyoxyalkylene glycol. Furthermore, even if the amount exceeds 10 parts by weight, no improvement in the antistatic effect is observed, and the object quality of the resulting composition deteriorates, and when it is made into fibers, its texture deteriorates. Become. The polyoxyalkylene glycol and/or
Alternatively, any method can be used to blend the alkyl sulfonic acid metal salt, and when both are used together, the polyester can be blended at the same time or in any order. That is, at any stage until the completion of molding of polyester, for example, before the start of the polycondensation reaction of polyester, during the polycondensation reaction, at the end of the polycondensation reaction when it is still in a molten state, in the powdered state, molding (spinning), etc. ) may be added alone or both at the same time or in any order. Further, both may be added after being melt-mixed in advance, or may be added in two or more portions, or both may be separately blended into polyester as planned and then mixed before molding or the like.
Furthermore, when it is added before the middle stage of the polycondensation reaction, it may be added after being dissolved or dispersed in a solvent such as glycol. In addition, the composition of the present invention may contain an oxidizing agent such as a sterically hindered phenol compound or a triazole compound, and it is preferable to do so. In addition, other antistatic agents as necessary,
Coloring agents, matting agents, other additives, etc. may be added. In particular, as described in Japanese Patent Publication No. 47-10246, it contains polyalkylene ether, metal salt derivatives of sulfonic acid, phosphonic acid, carboxylic acid, phosphoric acid, or phosphorous acid, and phenol derivatives with a boiling point of 280°C or higher. If you do so, you will get suitable results. Examples of the polyester polyether block copolymer comprising terephthalic acid and/or isophthalic acid, lower alkylene glycol, and polyalkylene glycol and/or its monoether used in the present invention include, for example, terephthalic acid-alkylene glycol-polyalkylene Examples include block copolymers such as glycol, terephthalic acid-isophthalic acid-alkylene glycol-polyalkylene glycol, terephthalic acid-alkylene glycol-polyalkylene glycol monoether, and terephthalic acid-isophthalic acid-alkylene glycol-polyalkylene glycol monoether. . Ethylene glycol, propylene glycol, tetramethylene glycol, and pentamethylene glycol are suitable as the alkylene glycol used for producing the block copolymer, and the polyalkylene glycol usually has an average molecular weight of 400 to 12,000, preferably
600 to 6000 polyethylene glycol, polyethylene glycol/polypropylene glycol copolymer, and polypropylene glycol are preferred.
Further, as the monoether of polyalkylene glycol, monoethyl ether, monomethyl ether, monophenyl ether, etc. of polyethylene glycol, polypropylene glycol, etc. are preferable, and monoethers of polyethylene glycol are particularly preferable. Further, it is particularly preferable that the block copolymer has a ratio of terephthalate units to isophthalate units in the range of 95:5 to 50:50 (molar ratio), and
It is particularly preferred that the molar ratio of terephthalate units+isophthalate units:polyalkylene glycol units is in the range of 3:1 to 10:1. Further, the average molecular weight of the block copolymer is usually 1,000 to 20,000, preferably 3,000 to 10,000, although it depends on the molecular weight of the polyalkylene glycol used. Although the block copolymer can be easily dispersed in water, it is preferable to add a small amount of a surfactant or an organic solvent to further improve the stability of the resulting aqueous dispersion. Furthermore, 0.2% of an ester-forming sulfonic acid alkali metal salt compound is added to the polyester comprising terephthalic acid or its ester-forming derivative, isophthalic acid or its ester-forming derivative, and lower alkylene glycol used in the present invention.
Polyethylene glycol 20-90 with ~40 mol% (based on dicarboxylic acid component) and average molecular weight 500-12000
It is necessary to use both terephthalic acid or its ester-forming derivative and isophthalic acid or its ester-forming derivative as the acid component of the polyester copolymer copolymerized in the amount by weight (based on the polymer produced). The molar ratio of the former and the latter is 95:5 ~
It is desirable that the ratio be within the 50:50 range. As the glycol component of this polyester copolymer, alkylene glycols such as ethylene glycol, propylene glycol, tetramethylene glycol, and pentamethylene glycol are preferably used. Examples of ester-forming alkali metal sulfonate compounds include alkali metals such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, and 4-sulfonaphthalene-2,7-dicarboxylic acid, and ester-forming derivatives thereof. In particular, 5-sulfoisophthalic acid, sodium salt and potassium salt of sulfoisophthalic acid are preferably used. The amount of these ester-forming sulfonic acid alkali metal salt compounds added is 0.2 to 40 mol%, preferably 5 to 20 mol%, based on the total carboxylic acid components. At less than 0.2 mol%,
The solubility of the produced polymer in water and the stability when it is made into a solution are significantly reduced, and the friction durability and entanglement durability of the fibers are reduced. Moreover, if it exceeds 40 mol %, the melt viscosity increases dramatically, making it difficult to obtain a desired highly polymerized polymer by melt polymerization. Furthermore, the polyalkylene glycol has a molecular weight of 500 to 12,000, preferably 600 to 6,000.
Preferred are polyethylene glycol, polyethylene glycol/polypropylene glycol copolymer, and polyprolene glycol. Furthermore, monoethers of polyalkylene glycol may be used; for example, monomethyl ethers, monoethyl ethers, monophenyl ethers, etc. of polyethylene glycol, polypropylene glycol, etc. are preferred, but monoethers of polyethylene glycol are particularly preferred. . The amount added is 20 to 90% by weight, preferably 30 to 80% by weight, based on the produced polymer. Any method can be used to attach the polyester polyether block copolymer and/or the polyester copolymer to the polyester fibers, but the most convenient method is to treat them as an aqueous dispersion. This treatment can be carried out in any step, but an effective method is to stretch the polyester fibers, then treat them with an aqueous dispersion and then heat treat them. The amount of the above polyester polyether block copolymer and/or the above polyester copolymer attached to the polyester fiber is
It is desirable that the amount is 0.02 to 2% by weight, preferably 0.04 to 1.5% by weight. There is no problem in using the block copolymer aqueous dispersion in combination with surfactants and other processing agents. Note that ordinary methods such as dipping and spraying can be used for attachment. The polyester fiber of the present invention may be a solid fiber, a hollow fiber, or a non-circular cross-section fiber.
Further, the polyester fiber of the present invention can be a sheath core type or side-by-side type conjugate fiber of a polyester blended with the aforementioned polyoxyalkylene glycol and/or alkyl sulfonate and a polyester not blended. In the case of a sheath core type composite fiber, a polyester containing polyoxyalkylene glycol and/or an alkyl sulfonate is placed in the sheath portion. At this time, in order to compensate for the slight decrease in crimp fastness caused by the addition of the third component, it is desirable to apply push crimp and/or three-dimensional crimp. Furthermore, the polyester fiber of the present invention may be a nonwoven fabric or a short fiber having a number of crimps of 13/25 mm or more.
It is preferable for use in sanitary materials, cotton stuffing, etc., and thereby improves friction durability and entanglement durability. In addition, it is desirable that the single fiber fineness is between 0.1 and 20 denier; if it is less than 0.1 denier, it will become too soft and its uses will be limited, and if it exceeds 20 denier, the entanglement will deteriorate and the single fibers will easily fall off from the web. Become. (Example) The present invention will be explained in more detail with reference to Examples below. In addition, in the examples, the antistatic durability was evaluated for raw cotton samples before washing and for samples washed for 300 minutes in a household washing machine with softened water at 30°C overflowing and a raw cotton spherical mass placed in a fine laundry net. The properties, friction durability, and entanglement durability were measured by the following methods. 1 Anti-static durability Samples before and after washing above at 25℃, relative humidity 65%
The specific resistance value was measured after being left for a day and night. The smaller the specific resistance value, the better the antistatic performance. 2 Friction Durability The higher the coefficient of friction (μ _S ) of the sample before and after washing is measured according to JIS L1015, the better. 3. Entanglement durability After carding the sample before and after washing to create a sliver, it was measured using a tensile tester as the pulling resistance in the longitudinal direction (unit: g/g: the value obtained by dividing the maximum pulling stress by the weight of the sliver). . Examples 1 to 6, Comparative Examples 1 to 2 A mixture of 100 parts of dimethyl terephthalate, 70 parts of ethylene glycol, and 0.025 parts of manganese acetate as a transesterification catalyst was heated with stirring and transesterified for 90 minutes while distilling off the generated methanol. I let it happen. Next, 0.015 part of phosphorous acid as a stabilizer and 0.041 part of antimony trioxide as a polycondensation catalyst were added, the temperature was raised to 285°C, and the system was reduced to a reduced pressure of 60 mmHg for 30 minutes, then 0.5 mmHg. Polycondensation reaction was carried out for 80 minutes under highly reduced pressure, and [η] was
In producing 0.65 polyethylene phthalate, various polyoxyalkylene glycols and/or sulfonic acid metal salts listed in Table 1 were added and blended. The obtained composition was once made into chips, dried according to a conventional method, and then spun at a spinning temperature of 1000 g/min using a spinneret having 1000 spinning holes with a diameter of 0.3 mm.
Spinning was carried out at 290°C and at a take-up speed of 1000 m/min. After that, 500,000 denier tow and plating, temperature 85℃, magnification
Stretched at 3.5 times. This drawn tow was treated in an aqueous polyester polyether block copolymer dispersion (3% by weight) having various compositions shown in Table 1, and crimped at 15 crimps/25 mm using a force crimper.
After heat treatment at 120°C, it was cut into a length of 51 mm.
The single fiber fineness of the obtained fibers was 3 denier, and the amount of each treatment agent applied was 0.35% by weight. Table 2 shows the results of evaluating the antistatic durability, friction durability, and entanglement durability of this fiber.

【table】

【table】

[Table] As is clear from the above results, the fibers of the present invention (Examples 1 to 6) exhibit good antistatic durability, friction durability, and entanglement durability; When not containing alkylene glycol and alkyl sulfonic acid metal salt (Comparative Example 2),
Alternatively, when the polyester polyether block copolymer was not attached (Comparative Example 1), the antistatic durability was poor, and the friction durability and entanglement durability were also poor. Examples 7 to 10, Comparative Example 3 100 parts of dimethyl terephthalate, 180 parts of 1,4-butanediol, 0.09 part of titanium tetrabutoxide as a catalyst, and Irganox 1076 as a stabilizer.
(manufactured by Ciba-Geigy) 0.1 part of the mixture was heated with stirring, and transesterification was carried out for 90 minutes while the generated methanol was distilled off. Then the reaction product
The system was kept at 240°C and the pressure inside the system was reduced, and finally polycondensation reaction was carried out for 90 minutes under a highly reduced pressure of 0.5 mmHg to obtain polybutylene terephthalate with [η] 0.60. Here, the inside of the system was returned to normal pressure with nitrogen gas, and 1 part of polyoxyethylene glycol having an average molecular weight of 10,000 and 4 parts of sodium dodecylsulfonate were added and mixed. The resulting composition was spun and stretched in the same manner as in Example 1, except that the spinning temperature was 280°C and the stretching temperature was 50°C. The obtained stretched tow was mixed with an aqueous polyester dispersion (7% by weight) obtained by copolymerizing ester-forming sulfonic acid alkali metal salt compounds of various compositions shown in Table 3 and polyester glycol so that the molecular weight was 6000. Thereafter, the same procedure as in Example 1 was carried out to obtain crimped fibers. The single fiber fineness of the obtained fibers was 3 denier, and the amount of each treatment agent applied was 0.3% by weight. About this fiber
Table 4 shows the results of evaluating antistatic durability, friction durability, and entanglement durability. For comparison, the measurement results for fibers that were not treated with the aqueous copolyester dispersion are also shown in Table 4 as Comparative Example 3.

[Table] Place

[Table] Example 13 In Example 1, instead of the aqueous polyether block copolymer dispersion, a 1:1 aqueous mixture of the polyether block copolymer of Example 1 and the polyester copolymer of Example 7 was used. The treatment was carried out under the same conditions as in Example 1 except that the dispersion was used.
The evaluation results of the obtained fibers are shown in Table 5, and they were found to have excellent performance.

[Table] (Effects of the Invention) The polyester fiber of the present invention has excellent antistatic durability, as well as improved friction durability and entanglement durability, and can be used as a filler for nonwoven fabrics, sanitary materials, quilting batting, etc. Suitable for use with cotton.

Claims (1)

[Claims] 1. The following general formula [In the formula, n represents an integer of 2 to 6. ] Polyester 100 mainly consisting of repeating units represented by
0.1 to 10 parts by weight of a polyoxyalkylene glycol substantially inert to the polyester and/or the following general formula RSO ₃ M [wherein R is an alkyl group having 8 or more carbon atoms, M is an alkali metal] shows. ] A polyester polyether made of terephthalic acid and/or isophthalic acid, lower alkylene glycol, polyalkylene glycol and/or its monoether, and a polyester fiber made by blending 0.5 to 10 parts by weight of an alkylsulfonic acid metal salt represented by Block copolymers and/
Or to a polyester consisting of terephthalic acid or its ester-forming derivative, isophthalic acid or its ester-forming derivative, and lower alkylene glycol, 0.2 to 40 mol% (based on the dicarboxylic acid component) of an ester-forming alkali metal sulfonic acid salt compound and an average of An antistatic polyester fiber attached with a polyester copolymer made by copolymerizing 20 to 90% by weight of polyethylene glycol with a molecular weight of 500 to 12,000 (based on the polymer produced), with a crimp count of 13.
KE/Antistatic polyester fiber, which is a staple fiber with a crimp of 25 mm or more.