JP2002155425A - Hygroscopic fiber and method for producing thermoplastic polyester-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hygroscopic fiber which is provided with excellent hygroscopic property and hydrophilicity and can be made inexpensive, and to provide a method for producing a thermoplastic polyester-based resin composition, by which the thermoplastic polyester-based resin composition can be simply and inexpensively produced. SOLUTION: This hygroscopic fiber comprises a thermoplastic polyester-based resin composition containing an N-vinylcarboxylic acid amide-based polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a hygroscopic fiber and a thermoplastic polyester resin composition.

[0002]

2. Description of the Related Art Hygroscopic fibers have high hygroscopicity and water absorbency as well as properties such as suppression of electrification, and are useful as materials for clothes and the like. As such a fiber, a nylon fiber containing polyvinylpyrrolidone (PVP) in nylon and imparting hygroscopicity by the hydrophilic property of PVP has been developed. However, such nylon fibers are relatively expensive, and there is room for contriving to apply them to a wide variety of uses by making them inexpensive.

[0003] On the other hand, thermoplastic polyesters have excellent basic properties such as heat resistance, strength and weather resistance and are relatively inexpensive. Therefore, they are industrially useful as materials for chemical products such as fibers, films and plastics. Widely used as a natural resin. By increasing the hygroscopicity of chemical products formed from such thermoplastic polyesters, for example,
It is expected as a moisture-absorbing fiber that replaces nylon fibers to which moisture has been imparted. In addition, by making the surface of the film or the like hydrophilic, for example, it is possible to prevent ink such as an aqueous pen or magic from repelling, and to impart these properties to a chemical product formed from a thermoplastic polyester. There is demand.

As a method for imparting hygroscopicity or hydrophilicity to a thermoplastic polyester, for example, it is known to graft-polymerize or soak the thermoplastic polyester with a water-soluble polymer such as polyethylene oxide. I have. However, in those manufactured by graft polymerization, there is room for devising more easily to impart hygroscopicity or hydrophilicity, and in those manufactured by immersion, the hygroscopicity or hydrophilicity is sufficiently increased or maintained. There was room for innovation.

JP-A-58-154721 discloses a fogging film made of a hydrophilic polyamide film or a hydrophilic polyester film. However, in this film, the hydrophilic compound may be contained in the form of a chemical bond to the film polymer or may be contained in a simple mixed form. Since it is disclosed that the reaction was carried out by graft polymerization of polyethylene oxide, while easily imparting moisture absorption and hydrophilicity,
There was room for devising these characteristics more reliably.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has excellent hygroscopicity and hydrophilicity.
Further, an object of the present invention is to provide a method for producing a thermoplastic polyester resin composition to which excellent hygroscopicity and hydrophilicity are imparted and which can be produced easily and at low cost.

[0007]

SUMMARY OF THE INVENTION The present invention is a hygroscopic fiber comprising a thermoplastic polyester resin composition containing an N-vinylcarboxylic acid amide polymer. The present invention is also a method for producing a thermoplastic polyester resin composition by melt-kneading a thermoplastic polyester and an N-vinylcarboxylic acid amide polymer.

The present inventors have studied various thermoplastic polyesters having excellent hygroscopicity and hydrophilicity, and found that fibers formed from the thermoplastic polyester contain an N-vinylcarboxylic acid amide polymer. By this, the effects of the thermoplastic polyester and the N-vinyl carboxylic acid amide-based polymer are synergistically exhibited, and excellent hygroscopicity and hydrophilicity are obtained without impairing basic performance such as heat resistance, strength, and weather resistance. First, attention is paid to the fact that it is possible to apply to a wide variety of uses at a lower cost than conventional nylon fibers to which water-absorbing properties are imparted. When a thermoplastic polyester-based resin composition is produced by melt-kneading a polymer and a thermoplastic polyester, excellent hygroscopicity and hydrophilicity are imparted, and moreover, Focusing on the fact that the thermoplastic polyester resin composition can be manufactured at low cost, it has been found that such a thermoplastic polyester resin composition can be suitably used as a material for chemical products such as fibers, films, and plastics. The inventors have conceived that they can solve the problem brilliantly, and have arrived at the present invention. Hereinafter, the present invention will be described in detail.

The hygroscopic fiber of the present invention is formed from a thermoplastic polyester resin composition. The thermoplastic polyester contained in the thermoplastic polyester resin composition is not particularly limited, for example, as an ester copolymer of glycol and acid, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexylene dimethylene Aromatic polyesters such as terephthalate, polyoxyethoxybenzoate, and polyethylene naphthalate; polyesters obtained by copolymerizing monomer components forming these aromatic polyesters with other acids and / or glycols; And aromatic polyester / polyether block copolymers and aromatic polyester / polylactone block copolymers formed using aromatic polyesters. Other acids include, for example, isophthalic acid,
Examples thereof include p-oxybenzoic acid, adipic acid, sebacic acid, glutaric acid, diphenylmethanedicarboxylic acid, and dimer acid. Examples of other glycols include hexamethylene glycol, diethylene glycol, neopentyl glycol, bisphenol A, neopentyl glycol alkylene oxide adducts, and the like. These may be used alone or in combination of two or more.

In the present invention, the thermoplastic polyester resin composition contains an N-vinyl carboxylic acid amide polymer. The N-vinylcarboxylic acid amide-based polymer is a polymer formed by polymerizing a monomer component containing an N-vinylcarboxylic acid amide-based monomer, and has properties such as high hygroscopicity and hydrophilicity. Having. Such polymers may be used alone or in combination of two or more.

The N-vinylcarboxylic acid amide-based monomer forming the N-vinylcarboxylic acid amide-based polymer includes, for example, the following general formula (1):

[0012]

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(Wherein, R ¹ represents hydrogen or a methyl group. R ² and R ³ are the same or different and represent hydrogen, a methyl group or an ethyl group, and R ² and R ³ are May form an alkylene group having 3 to 5 carbon atoms).

Specific examples of the N-vinylcarboxylic acid amide-based monomer include N-vinylacetamide and N-vinylacetamide.
Methyl-N-vinylacetamide, N-vinylformamide, N-methyl-N-vinylformamide, N-vinylpropionamide, N-vinylpyrrolidone and the like can be mentioned, and one kind or two or more kinds can be used as needed.

In the monomer component forming the N-vinyl carboxylic acid amide polymer, it is preferable that the N-vinyl carboxylic acid amide monomer is contained as a main component. It may or may not be included. For example, the total amount of the monomer components is 100% by weight.
In this case, the content is preferably 50% by weight or more. 50
When the amount is less than the weight%, the function and effect of the present invention may not be sufficiently exhibited. More preferably, 70
% By weight, more preferably 90% by weight or more. The N-vinyl carboxylic acid amide monomer is 1
Seeds may be used, or two or more kinds may be used. When a monomer component containing two or more types of monomers is polymerized, the polymerization form is not particularly limited, and may be, for example, any of block, alternating, and random. .

The monomer other than the N-vinyl carboxylic acid amide monomer contained in the above monomer component is not particularly limited, and is a polymerizable polymer copolymerizable with the N-vinyl carboxylic acid amide monomer. Monomers, specifically, for example,
(1) (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate; (2) ) (Meta)
Acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, N, N-
(Meth) acrylamide derivatives such as dimethyl (meth) acrylamide; (3) basic unsaturated monomers such as dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, vinylpyridine, vinylimidazole and the like; Salts or quaternary compounds; (4) vinylamides such as vinylformamide, vinylacetamide and vinyloxazoline; and (5) carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, itaconic acid, maleic acid and fumaric acid. (6) unsaturated anhydrides such as maleic anhydride and itaconic anhydride; (7) vinyl acetate;
Vinyl esters such as vinyl propionate; (8) vinyl ethylene carbonate and its derivatives; (9) styrene and its derivatives; (10) (meth) acrylic acid-2-
(11) vinyl sulfonic acids and derivatives thereof; (12) vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether; and (13) olefins such as ethylene, propylene, octene and butadiene. Can be
These may be used alone or in combination of two or more.

In the present invention, the N-vinylcarboxylic acid amide-based polymer is preferably an N-vinylpyrrolidone-based polymer. Thereby, it is possible to more reliably exert the operation and effect of the present invention. The N-vinylpyrrolidone-based polymer is a polymer formed by using N-vinylpyrrolidone as an N-vinylcarboxylic amide-based monomer in a monomer component forming an N-vinylcarboxylic amide-based polymer. is there.

The method for producing the N-vinyl carboxylic acid amide polymer is not particularly limited, and examples thereof include an aqueous solution polymerization method, a solution polymerization method in an organic solvent, a reversed phase suspension polymerization method, an emulsion polymerization method, A precipitation polymerization method and the like can be mentioned, and the reaction conditions and the like during the polymerization are not particularly limited. The polymerization initiator used is not particularly limited, and one or more conventionally known polymerization initiators can be used, and the amount used is not particularly limited. Also, without using a polymerization initiator, heat,
A polymerization method using light or radiation may be used.

The molecular weight of the N-vinyl carboxylic acid amide polymer is, for example, 1000
It is preferably from 5,000,000 to 5,000,000. If it is less than 1,000, the mechanical strength of the hygroscopic fiber may be insufficient, and if it exceeds 5,000,000, the workability at the time of forming the hygroscopic fiber may not be sufficient. More preferably, it is 5,000 to 1,000,000, and still more preferably, it is 10,000 to 500,000.

The content of the N-vinylcarboxylic acid amide-based polymer is, for example, 0.5 to 30% by weight based on 100% by weight of the thermoplastic polyester resin composition.
It is preferable that If the content is less than 0.5% by weight, the hygroscopicity of the hygroscopic fiber may not be sufficiently improved,
If it exceeds 0% by weight, the basic properties such as heat resistance, strength and weather resistance of the hygroscopic fiber may be reduced. More preferably, it is 1 to 25% by weight, and still more preferably, 5 to 20% by weight.
% By weight.

The thermoplastic polyester resin composition may contain one or more compounds other than those described above. Such compositions include, for example, matting agents,
Pigments, light stabilizers, heat stabilizers, antioxidants, antistatic agents,
Dyeability improvers and the like.

As a method for producing the hygroscopic fiber of the present invention, usually, a thermoplastic polyester, an N-vinylcarboxylic acid amide polymer and a blended compound as required are mixed to form a thermoplastic polyester fiber. Fibers are formed (yarn-formed) as a resin composition. As a spinning method, for example, after spinning, cooling, and refueling, the spinning speed is 1
Direct spinning drawing method of drawing at 000 m / min or more, drawing and winding without winding once; normal melt spinning such as high-speed spinning method of drawing at a high speed of 3000 m / min or more and winding without drawing It can be performed by the method. The cross-sectional shape of the single yarn of the hygroscopic fiber produced in this way is
There is no particular limitation as long as it is appropriately set according to the intended use and the like, and examples thereof include a round cross section; The thickness of the single yarn is not particularly limited.

In the method for producing the thermoplastic polyester resin composition of the present invention, the thermoplastic polyester and the N-vinyl carboxylic acid amide polymer are melt-kneaded. Such a step of melt-kneading is also referred to as a melt-kneading step in this specification. In the present invention, steps other than the melt-kneading step may be appropriately included according to the intended use of the thermoplastic polyester-based resin composition.

The above-mentioned melt-kneading step is carried out by melt-kneading an N-vinylcarboxylic acid amide-based polymer as an essential component together with the thermoplastic polyester. Examples of the thermoplastic polyester and the N-vinyl carboxylic acid amide-based polymer include the same ones as described above, and one or more of them can be used. Moreover, you may use the compound as mentioned above. These contents are appropriately set according to the intended use of the thermoplastic polyester resin composition.

The above-mentioned melt-kneading step can be carried out, for example, by melt-kneading a thermoplastic polyester and an N-vinyl carboxylic acid amide-based polymer with a kneading machine. In such a kneading method, it is preferable to knead in a heated state. Examples of the mixer include a kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, and a kneading roll; a Henschel mixer; and the kneading temperature may be appropriately set according to the kneader or the like. ,
For example, the temperature is preferably set to 180 to 340 ° C. When kneading, the compounds may be charged all at once or separately.

In the process for producing the thermoplastic polyester resin composition of the present invention, the thermoplastic polyester is melt-kneaded with the N-vinyl carboxylic acid amide polymer, so that the thermoplastic polyester is added to the solution containing the water-soluble polymer. Can provide superior hygroscopicity and continuity of hydrophilicity compared to the case of immersion, and can be more easily and inexpensively compared with the case where a water-soluble polymer is graft-polymerized to a thermoplastic polyester. Products can be manufactured. The thermoplastic polyester-based resin composition produced in this manner can be suitably applied as, for example, a material for chemical products such as fibers, films, and plastics. Among these, it is suitable as a material capable of forming the hygroscopic fiber of the present invention. That is, a method for producing a hygroscopic fiber including a melt kneading step of a thermoplastic polyester, wherein the melt kneading step is performed by melt kneading a thermoplastic polyester and an N-vinyl carboxylic acid amide polymer. The method for producing a conductive fiber is also one of the preferred embodiments of the present invention.

When the thermoplastic polyester-based resin composition is used as a fiber material, the yarn can be formed in the same manner as described above. It can be molded by a commonly used molding method such as injection molding and blow molding. The chemical product thus obtained is industrially useful because it has excellent hygroscopicity and hydrophilicity and is inexpensive.

[0028]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 A thermoplastic polyester and a water-soluble resin shown in Table 1 were melt-kneaded by a twin-screw extruder, and the obtained resin composition was formed into a film by a press to obtain a sample. After drying at 140 ° C. for 3 hours under reduced pressure using a vacuum dryer, weight change when left standing in a thermo-hygrostat at predetermined conditions (20 ° C., 65% RH or 30 ° C., 65% RH) for 24 hours. Was measured, and the moisture absorption was determined. The results are shown in Table 1. (Kneading conditions) Apparatus: twin screw extruder (φ = 29.75 mm, L / D =
30, barrel temperature 250 ° C, rotation speed 120rpm)

The moisture absorption (%) was calculated by the following equation. In the following formula, the weight after drying is 3 at 140 ° C.
It is the weight after time drying, and the weight after treatment is the weight after standing in a thermo-hygrostat under predetermined conditions for 24 hours. [Moisture absorption (%)] = {(AB) / B} × 100 A: Weight after treatment B: Weight after drying

Comparative Examples 1-2 A thermoplastic polyester and a water-soluble resin having the composition shown in Table 1 were melt-kneaded in the same manner as in Example 1 to produce a resin composition. Using this, a film was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0032]

[Table 1]

Table 1 is described below. PBT is a thermoplastic polyester polybutylene terephthalate (trade name "Novadol 5010", manufactured by Polyplastics), and PVP is a water-soluble resin polyvinylpyrrolidone (trade name "K-30", Wako Pure Chemical Industries, Ltd.) Industrial company)
And PEO is a water-soluble resin polyethylene oxide (trade name “Alcox R400”, manufactured by Meisei Chemical Co., Ltd.).

[0034]

As described above, the hygroscopic fiber of the present invention has excellent hygroscopicity and hydrophilicity because it has the above-mentioned structure, and can be made inexpensive. Further, the method for producing the thermoplastic polyester resin composition of the present invention,
Excellent hygroscopicity and hydrophilicity are imparted, and it can be easily and inexpensively manufactured. The thermoplastic polyester resin composition obtained thereby can be suitably used as a material for fibers, films, plastics and the like. You can do it.

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Claims (2)

[Claims] 1. A hygroscopic fiber comprising a thermoplastic polyester resin composition containing an N-vinyl carboxylic acid amide polymer. 2. A method for producing a thermoplastic polyester resin composition, comprising melt-kneading a thermoplastic polyester and an N-vinylcarboxylic acid amide polymer.