JP2001279523A - Vinyl chloride-based resin composition for fiber and stabilizer composition for vinyl chloride-based resin for fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both a vinyl chloride resin composition for yarn having excellent spinnability in melt spinning, capable of producing a yarn having a fine size, hardly causing end breakage, burn mark and uneven coloring, extremely improving initial discoloration and providing a yarn to hardly cause end breakage and a stabilizer composition for a vinyl chloride-based resin for a yarn. SOLUTION: This vinyl chloride-based resin composition for a yarn comprises (a) 0.01-10 pts.wt. of at least one kind of hydrotalcite compound and (b) 0.001-1 pt.wt. of at least one silicic acid compound based on 100 pts.wt. of a vinyl chloride-based resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition for fibers and a stabilizer composition for vinyl chloride resin for fibers, and more particularly to artificial hair for hair decoration such as wigs, blades and extension hair. The present invention relates to a vinyl chloride resin composition for a fiber and a stabilizer composition for a vinyl chloride resin for a fiber, which can be used as a fiber for forming a vinyl chloride fiber having gloss, hue, and texture similar to human hair.

[0002]

2. Description of the Related Art A vinyl chloride fiber formed by spinning a vinyl chloride resin into a fibrous form is excellent in transparency and flexibility, and therefore is used for artificial hair such as hair decoration. It is often used as a fiber for hair. However, the vinyl chloride resin has a high melt viscosity, is thermally decomposed at a high temperature, and has extremely low spinnability at a high draw ratio, so that it is difficult to spin fine fibers by melt spinning. For this reason, in general, a method of producing by a wet or dry spinning method using a solvent, or a special method, for example, as described in JP-B-34-6908, immediately melts a yarn eluted from a nozzle. A method of improving the spinnability and stretching at a high draw ratio to obtain a fine fiber by improving the spinnability by introducing the fiber into a high-temperature heat medium or instantaneously heating and melting through a heating spinning tube provided in the fiber axis direction. Are known. Also, as described in JP-B-51-2109, a study has been made to improve spinnability by using a chlorinated vinyl chloride resin and a methyl methacrylate-based polymer in combination.

[0003] However, even with the above-mentioned method, there is a problem that the vinyl chloride resin cannot obtain sufficient spinnability in melt spinning, and it is difficult to obtain sufficiently fine fine fibers. In addition, the vinyl chloride resin undergoes a dehydrochlorination reaction due to the action of heat at a high temperature or irradiation with light such as sunlight or ultraviolet light to form a polyene structure,
Yellowing occurs. The yellowing proceeds with time due to the heat history during processing, and causes "burn" and "color unevenness",
The vinyl chloride fiber obtained by spinning the vinyl chloride resin has a problem that the coloring property, particularly the initial coloring property, is inferior and the commercial value may be reduced. Further, for example, the molten resin used in spinning, such as in a melt spinning extruder, sticks and becomes a stagnant substance, which may be thermally decomposed to generate a burnt resin. Spinning becomes difficult and cleaning requires a long time.

In order to solve such a problem, Japanese Patent Application Laid-Open No. Hei 10-251916 discloses a fiber composition comprising a mixture of a vinyl chloride resin and a chlorinated vinyl chloride resin mixed with an organotin stabilizer and a lubricant. A vinyl chloride resin composition has been proposed, and although problems such as "burn" and "color unevenness" have been improved, the organotin-based stabilizer used here is considered to have an adverse effect on the environment. There was also the problem of odor.
JP-A-11-100714 proposes a vinyl chloride resin for fibers in which a vinyl chloride resin is blended with an ethylene-vinyl acetate resin, a heat stabilizer and a lubricant. Organotin-based stabilizers used as heat stabilizers have a problem of odor, and when a stabilizer other than the organic tin-based stabilizers specifically exemplified is used, "burn" or "color" Satisfactory performance has not yet been obtained in terms of improvement of "unevenness". For example, when the hydrotalcite compound or the like used here is used alone, poor dispersion occurs, "thread breakage" occurs, and the effect of improving "burn" and "uneven color" is small.

The present invention has been made in view of the above-mentioned problems, and has excellent spinnability during melt spinning, enables production of fine-fiber fibers, and provides "cut yarn" and "burnt". Vinyl resin composition for fiber and stabilizer composition for vinyl chloride resin for fiber that can hardly cause color unevenness and can significantly improve initial coloring property and can provide fiber that hardly causes thread breakage The purpose is to provide.

[0006]

Means for Solving the Problems The present inventors have made intensive studies and as a result, have found that by using a vinyl chloride resin in combination with a hydrotalcite compound and a silicic acid compound, "thread breakage" and "burning" can be achieved. The present inventors have found that a vinyl chloride fiber having no unevenness or "color unevenness" can be provided, and arrived at the present invention.

That is, the present invention relates to a vinyl chloride resin 100
(1) 0.001 to 10 parts by weight of at least one hydrotalcite compound and (b) 0.001 to 10 parts by weight of at least one silicate compound. It is intended to provide a vinyl resin composition.

The present invention also relates to (a) 100 parts by weight of a hydrotalcite compound, and (b) 0.1% of a silicate compound.
It is intended to provide a stabilizer composition for a vinyl chloride resin for fibers, characterized in that the stabilizer composition contains from 50 to 50 parts by weight.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the vinyl chloride resin composition for fibers and the stabilizer composition for vinyl chloride resin for fibers of the present invention will be described in detail.

The hydrotalcite compound of the component (a) used in the present invention is, as represented by the following general formula (I), a composite salt comprising magnesium and / or an alkali metal and aluminum or zinc, magnesium and aluminum. It may be a compound which is obtained by dehydrating water of crystallization.

[0011]

Embedded image (Wherein Ia represents an alkali metal atom, x1, x2
And y are in the following ranges, respectively, and m represents 0 or a positive number; 0 ≦ x2 / x1 <10, 2 ≦ x1 + x2 ≦ 20)

The hydrotalcite compound may be a natural product or a synthetic product. The method for synthesizing the synthetic product is described in JP-B-46-2280, JP-B-50-30039, and JP-B-51-29129.
Gazette, Japanese Patent Publication No. 3-36839, JP-A-61-174
Known methods described in, for example, Japanese Patent Application Laid-Open No. 270, JP-A-5-17952 and the like can be exemplified. Further, the hydrotalcite compound can be used without being limited by its crystal structure, crystal particle diameter, and the like.

The surface of the hydrotalcite compound may be a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic metal sulfonate such as an alkali metal dodecylbenzenesulfonate, or a higher salt thereof. It may be one coated with a fatty acid amide, a higher fatty acid ester or a wax.

The compounding amount of the hydrotalcite compound (a) is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably 0 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin. 0.1 to 5 parts by weight. If the compounding amount is less than 0.01 part by weight, the heat stabilizing effect cannot be obtained,
Further, it is not preferable to mix more than 10 parts by weight, because not only is it wasteful, but there is a possibility that coloring may be reduced.

The silicate compound (b) used in the present invention may be an alkali metal such as sodium, an alkaline earth metal such as calcium or magnesium, or a silicate such as aluminum. It is preferable to use it because a synergistic effect with the hydrotalcite compound is exhibited. The silicon dioxide used here has a purity of preferably 90% or more, more preferably 95% or more, and may be anhydrous or hydrated. The specific surface area of silicon dioxide is 80 m ² / g or more,
It is preferably at least 120 m ² / g.

The amount of the silicate compound (b) is 0.001 to 100 parts by weight of the vinyl chloride resin.
To 1 part by weight, preferably 0.005 to 0.5 part by weight, more preferably 0.01 to 0.1 part by weight. If the compounding amount is less than 0.001 part by weight, no compounding effect is obtained, and
It is not only useless to mix more than parts by weight,
It is not preferable because there is a possibility that coloring may be reduced.

These components (a) and (b) can be used alone in the vinyl chloride resin.
Mixing in advance with a Henschel mixer or the like and blending it as a stabilizer composition is preferable because secondary aggregation is suppressed, excellent dispersibility is exhibited, and the effect of improving heat resistance can be remarkably exhibited.

The method for producing the stabilizer composition is not particularly limited, and is a method of mixing the components (a) and (b) and then adding other additives or mixing the components (a) and (b). And a method of mixing other additives together with the component (ii). The mixing may be carried out by using a mixing device such as the above-mentioned Henschel mixer, rocking mixer, ribbon blender, super mixer, raiger or the like, or by manually blending in a container.

In this case, the amount of component (b) is 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, per 100 parts by weight of component (a). Parts by weight. If the compounding amount is less than 0.1 part by weight, it is not preferable because the synergistic effect with the hydrotalcite compound is insufficient, and if the compounding amount exceeds 50 parts by weight, it is useless, It is not preferable because the stabilizing action of the hydrotalcite compound may be impaired when blended with the resin.

The vinyl chloride resin used in the present invention is not particularly limited to a polymerization method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. Examples thereof include polyvinyl chloride and chlorinated polyvinyl chloride. , Vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride
Propylene copolymer, vinyl chloride-styrene copolymer,
Vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene copolymer , Vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer Vinyl chloride resins such as polymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-various vinyl ether copolymers, and their mutual blended products, or those vinyl chloride resins and other chlorine-free synthetic resins For example, acrylonitrile-styrene copolymer, acrylonitrile-styrene -Blends with butadiene terpolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer, polyester, polyvinylidene chloride, chlorinated polyethylene, etc., block copolymers, graft copolymers Coalescence and the like.

The vinyl chloride resin composition or the stabilizer composition for a vinyl chloride resin of the present invention preferably contains a zinc salt of an organic acid, since initial coloring can be suppressed.

Here, examples of the organic acid include carboxylic acids, phenols and organic phosphoric acids. The zinc salt of an organic acid may be a normal salt, an acidic salt, a basic salt or an overbased salt.

Examples of the carboxylic acids include caproic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid,
Isostearic acid, 12-hydroxystearic acid, chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linoleic acid, oleic acid, arachinic acid, behenic acid, erucic acid, brassic acid and similar acids and Tallow fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids, cottonseed oil fatty acids, and other naturally occurring mixtures of the above acids, benzoic acid, p-tert-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid,
Toluic acid, xylic acid, salicylic acid, 5-tert-octylsalicylic acid, naphthenic acid, cyclohexanecarboxylic acid, adipic acid, maleic acid, acrylic acid, methacrylic acid and the like, and the phenols include, for example, phenol, Cresol, ethyl phenol, cyclohexyl phenol, nonyl phenol, dodecyl phenol and the like are mentioned, and as the organic phosphoric acid, for example, mono- or di-octyl phosphoric acid, mono- or di-dodecyl phosphoric acid, mono- or di-octadecyl phosphoric acid, mono- or di (nonyl phenyl) Examples include phosphoric acid, nonylphenyl phosphonate, stearyl phosphonate, and the like.

In the vinyl chloride resin composition of the present invention, the compounding amount of the organic acid zinc salt is 100 parts by weight of the vinyl chloride resin.
0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on parts by weight.
It is 0.5 to 5 parts by weight. If the compounding amount is less than 0.01 part by weight, no compounding effect is obtained, and if the compounding amount is more than 10 parts by weight, not only is it not only useless but also blackening may occur in a short time during heat history, which is not preferable. .

In the stabilizer composition of the present invention, the amount of the organic acid zinc salt is 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the hydrotalcite compound (a). Department. When the amount is less than 0.1 part by weight or more than 50 parts by weight, the same problem as described above occurs.

The vinyl chloride resin composition or the stabilizer composition for a vinyl chloride resin of the present invention preferably contains a β-diketone compound, so that the initial coloring can be suppressed.

Here, the β-diketone compound is, for example, dibenzoylmethane, benzoylacetone, stearoylbenzoylmethane, caproylbenzoylmethane, dehydroacetic acid, tribenzoylmethane, 1,3-bis (benzoylacetyl) benzene, or the like. (Lithium, sodium, potassium, calcium, magnesium, barium, zinc, etc.).

In the vinyl chloride resin composition of the present invention, the amount of the β-diketone compound is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the vinyl chloride resin. It is. If the compounding amount is less than 0.01 part by weight, no compounding effect is obtained, and if the compounding amount is more than 10 parts by weight, not only is it not only useless but also blackening may occur in a short time during heat history, which is not preferable. .

Further, in the stabilizer composition of the present invention, β
The amount of the diketone compound is 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the hydrotalcite compound (a). When the amount is less than 0.1 part by weight or more than 50 parts by weight, the same problem as described above occurs.

The vinyl chloride resin composition of the present invention may further contain various additives usually used as additives for vinyl chloride resins, for example, organic acid alkaline earth metal salts, organic tin compounds, Plasticizers, lubricants, anti-fog agents, anti-fog agents,
Compounding liquid polybutadiene, perchlorates, zeolite compounds, organic phosphite compounds, phenolic or sulfuric antioxidants, epoxy compounds, polyols, ultraviolet absorbers, hindered amine light stabilizers, other inorganic metal compounds, etc. You can also.

Examples of the alkaline earth metal constituting the alkaline earth metal salt of an organic acid include magnesium, calcium, barium, strontium and the like, and specific examples of the organic acid include the above-mentioned component (b). The alkaline earth metal salt of an organic acid may be a normal salt, an acidic salt, a basic salt or an overbased salt.

Examples of the organotin compound include laurate, malate and dibutyltin or dioctyltin.
Mercapto, malate polymers, and the like.

Examples of the plasticizer include dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, and the like.
Phthalic acid-based plasticizers such as dicyclohexyl phthalate and dioctyl terephthalate; adipic acid-based plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, and di (butyldiglycol) adipate; ethylene glycol, diethylene glycol, and triethylene glycol as polyhydric alcohols , 1,2-
Propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol and the like, and as a dibasic acid,
Use oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc., and if necessary, monohydric alcohol and monocarboxylic acid. Polyester plasticizer used for the stopper: triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri (butoxyethyl) phosphate, octyl diphenyl phosphate And other phosphate ester plasticizers; other, tetrahydrophthalic acid plasticizers, azelaic acid plasticizers, sebacic acid plasticizers, stearic acid plasticizers, citric acid plasticizers, and trimellitic acid plasticizers. , Pyromellitic acid plasticizers include biphenylene polycarboxylic acid plasticizers.

Examples of the lubricant include hydrocarbon lubricants, fatty acid lubricants, fatty acid amide lubricants, fatty acid ester lubricants, alcohol lubricants, metal soap lubricants and the like.

Examples of the antifogging agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol monopalmitate, polyethylene glycol monostearate, and polyoxyethylene sorbitan monolaurate. , Polyoxyethylene sorbitan monopalmitate, glycerin monolaurate, glycerin monopalmitate, glycerin monostearate, glycerin monooleate, pentaerythritol monolaurate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan distearate,
Diglycerindiolate sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium butylnaphthalenesulfonate, cetyltrimethylammonium chloride, dodecylamine hydrochloride, lauric lauramide ethyl phosphate, triethylcetylammonium iodide, oleylaminodiethylamine hydrochloride And dodecylpyridinium salts.

Examples of the above antifoggant include an anionic fluorinated surfactant, a cationic fluorinated surfactant,
Examples include amphoteric fluorinated surfactants, nonionic fluorinated surfactants, and fluorinated compounds such as fluorinated oligomers.

Examples of the liquid polybutadiene include 1,2-atactic polybutadiene, 1,2-syndiotactic polybutadiene, 1,2-isotactic polybutadiene, and 1,1-atactic polybutadiene obtained by homopolymerization of 1,3-butadiene. 4-cis polybutadiene, 1,
4-trans polybutadiene, or a block polymer, a graft polymer and a mixture thereof, further partially epoxidized, one having a hydroxyl group and / or a carboxyl group at a terminal, or partially maleated;
Modified products such as halogenated, boiled, hydrogenated, acrylic-modified, urethane-modified, and ester-modified are mentioned. Among these liquid polybutadienes, epoxy-modified ones are particularly preferred since they have the effect of improving weather resistance. The average molecular weight of these liquid polybutadienes is preferably 2
50 to 25000, more preferably 500 to 1000
0.

The above perchlorates include lithium perchlorate, sodium perchlorate, potassium perchlorate, strontium perchlorate, barium perchlorate, zinc perchlorate,
Aluminum perchlorate, lead perchlorate, ammonium perchlorate, etc., and these perchlorates may be anhydrous or hydrated.Alcohols and esters such as butyl diglycol, butyl diglycol adipate, etc. It may be one dissolved in a system solvent or the like and a dehydrated product thereof.

The zeolite compound is an alkali or alkaline earth metal aluminosilicate having a unique three-dimensional zeolite crystal structure.
Type, X type, Y type, and P type zeolite, monodenite,
Analsite, sodalite group aluminosilicate, clinbutyrolite, erionite, chabazite and the like can be mentioned, and the hydrate or crystallization water containing crystal water of these zeolite compounds (so-called zeolite water) is removed. Any of anhydrides may be used.

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, Tris (mono- and di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) .ethyl phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-di Tributylphenyl) octyl phosphite, diphenyldecyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite,
Dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol)
1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertbutyl-4-)
Methylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenol pentaerythritol diphosphite, tetra (C
₁₂ - ₁₅ mixed alkyl) -4,4 '- isopropylidene diphenyl phosphite, bis [2,2'-methylenebis
(4,6-Diamylphenyl)] • isopropylidenediphenyl phosphite, hydrogenated-4,4′-isopropylidenediphenol polyphosphite, bis (octylphenyl) bis [4,4′-n-butylidenebis ( 2-
Tert-butyl-5-methylphenol)] • 1,6-hexanediol • diphosphite, tetratridecyl • 4,4
4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl).
1,1,3-tris (2-methyl-5-tert-butyl-4
-Hydroxyphenyl) butane triphosphonite,
Examples thereof include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol, 2,4,6-tritert-butylphenol monophosphite, and the like.

Examples of the phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-p-cresol.
Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,3 5-di-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-tert-butyl-m -Cresol), 2-octylthio-4,6-di (3,5-ditert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol) , Bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid]
Glycol ester, 4,4'-butylidenebis (4,
6-di-tert-butylphenol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 1,1,3
-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) Phenyl] terephthalate, 1,3,5-
Tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)
Isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert. Tributyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl- 6- (2-Acroyloxy-3-tert-butyl-
5-methylbenzyl) phenol, 3,9-bis [2-
(3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl]-
2,4,8,10-tetraoxaspiro [5.5] undecane] and triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

Examples of the sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecylmercaptopropionate). And β-alkyl mercaptopropionates of polyols.

Examples of the epoxy compound include epoxidized animal and vegetable oils such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized tallow oil, epoxidized castor oil, epoxidized safflower oil, and the like. Epoxidized methyl stearate, epoxidized butyl stearate, epoxidized 2-ethylhexyl stearate, epoxidized stearyl stearate, epoxidized polybutadiene, tris (epoxypropyl)
Isocyanurate, epoxidized tall oil fatty acid ester, epoxidized linseed oil fatty acid ester, vinylcyclohexene diepoxide, dicyclohexene carboxylate, 3,4-epoxycyclohexene methyl epoxy cyclohexane carboxylate, bisphenol A
Diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerin polyglycidyl ether, hexanediol polyglycidyl ether, 2,2
-Dimethyl-1,3-propanediol polyglycidyl ether, hydrogenated bisphenol polyglycidyl ether, cyclohexanedimethanol polyglycidyl ether and the like.

Examples of the polyols include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, pentaerythritol or dipentaerythritol half-ester stearic acid, bis (dipentaerythritol) adipate, Glycerin,
Tris (2-hydroxyethyl) isocyanurate, sorbitol, mannitol, trehalose and the like can be mentioned.

As the above-mentioned ultraviolet absorber, for example,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4 '-(2-methacryloyloxyethoxyethoxy) benzophenone, 5,5'-methylenebis (2-hydroxy-4 2-hydroxybenzophenones such as -methoxybenzophenone); 2- (2-hydroxy-5-
Methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- ( 2-hydroxy-3-tert-butyl-5-methylphenyl) -5
-Chlorobenzotriazole, 2- (2-hydroxy-
3-dodecyl-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl -5-C ₇
~ ₉ mixed alkoxycarbonylethylphenyl) triazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole; 2- (2-hydroxy-4
-Hexyloxyphenyl) -4,6-diphenyl-1,
3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6 -Bis (2,4-dimethylphenyl)-
1,3,5-triazine, 2- (2-hydroxy-4-
2- (2-hydroxyphenyl) -1,3,5- such as acryloyloxyethoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine
Triazines; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-
3,5-di-tert-butyl-4-hydroxybenzoate,
2,4-di-tert-amylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5
Benzoates such as di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano- and cyanoacrylates such as β, β-diphenylacrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, , 2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,
2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octoxy-2,
2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-)
Piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis ( 2,2,6,6-tetramethyl-4-piperidyl) .bis (tridecyl) -1,
2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2-
(3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,
6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1, 6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4
-Dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4
-Piperidylamino) hexane / 2,4-dichloro-6
Tertiary octylamino-s-triazine polycondensate, 1,
5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1, 5,
8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2
2,6,6-pentamethyl-4-piperidyl) amino)
-S-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6 -Tetramethyl-4-piperidyl) amino-s-triazin-6-ylamino] undecane, 1,6,11-tris [2,4-
Bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino-s-triazine-6
-Ylamino] undecane, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4 , 8,10-Tetraoxaspiro [5.5] undecane, 3,9-bis [1,
1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy)
Butylcarbonyloxydiethyl] -2,4,8,10
-Tetraoxaspiro [5.5] undecane and the like.

The above-mentioned other inorganic metal compounds include
Examples include calcium phosphate, calcium oxide, calcium hydroxide, magnesium phosphate, magnesium oxide, magnesium hydroxide and the like.

Further, the vinyl chloride resin composition of the present invention may contain other stabilizing aids usually used for vinyl chloride resins. Examples of such a stabilizing aid include diphenylthiourea, diphenylurea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, p-tert-butylbenzoic acid, and the like.

In addition, the vinyl chloride resin composition of the present invention may contain, if necessary, additives usually used for vinyl chloride resins, such as fillers, coloring agents, crosslinking agents, antistatic agents, and plate-outs. Inhibitors, surface treatment agents, lubricants, flame retardants, fluorescent agents, fungicides, bactericides, metal deactivators, release agents, pigments, processing aids, antioxidants, light stabilizers, foaming agents, etc. Can be blended.

The method for producing vinyl chloride resin-based fibers using the vinyl chloride-based resin composition of the present invention is not particularly limited, but is mixed using a mixing equipment such as a ribbon blender or a Henschel mixer. Then, the obtained mixture is directly charged into an extruder in a powder state and melt-spun.
In addition, a method of granulating with an extruder, a kneader, a continuous roll, or the like to obtain a spinning raw material, and then spinning may be used.

The vinyl chloride resin fibers obtained by using the vinyl chloride resin composition of the present invention include, for example, wigs,
It can be used in applications such as artificial hair fibers for head decoration such as blades and extension hair.

[0052]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples.

Examples 1-1 to 1-5 (Examples of preparation of stabilizer composition) 72.6 parts by weight of a hydrotalcite compound (HT-1 or HT-2) and Carplex # 80 (Shionogi Pharmaceutical Co., Ltd.) 2.2 parts by weight of water-containing amorphous silicon dioxide (produced by K.K.) were charged into a Henschel mixer, kneaded at 350 rpm for 2 minutes, and further 1050.
The mixture was kneaded at rpm for 5 minutes. Thereafter, the other components (Table 1) were charged and kneaded at 1,050 rpm for 5 minutes, and then taken out. The bulk specific gravity of the stabilizer composition was measured. The results are shown in Table 1.

[Comparative Examples 1-1 and 1-2] (Production Examples of Stabilizer Compositions A and B) The ingredients (Table 1) were charged all at once into a Henschel mixer, and 350 rpm.
And then kneaded at 1050 rpm for 10 minutes and then taken out. The bulk specific gravities of the stabilizer compositions A and B were measured. The results are shown in Table 1.

[0055]

[Table 1]

[Examples 2-1 to 2-6 and Comparative Example 2-1]
~ 2-3] The following formulation was cut at a resin temperature of 130 ° C, 60
The mixture was cooled and cooled with a 75-liter Henschel mixer under discharge conditions, and melt-spun under the following extrusion conditions.

(Blending) Parts by weight Vinyl chloride resin (manufactured by Taiyo PVC Co., Ltd .; average degree of polymerization: 1050) 100 Stabilizer composition (Table 1) 3 Epoxidized soybean oil (manufactured by Asahi Denka Kogyo KK; O-130P) 1) Phosphorus chelator (Adeka Stab 1030 manufactured by Asahi Denka Kogyo Co., Ltd.) 0.3 Polyethylene wax (Mitsui Petrochemical Co., Ltd.) 0.5

(Extrusion conditions) Screw: screw diameter 40 mm, L / D = 2
5, compression ratio 2.3: 1, screw type [40 mm pitch, full flight type] Nozzle: hole shape; glasses, hole area: 0.0509 mm
2, number of holes; 120, arrangement of holes; three rows of circles, land length of nozzle holes; 0.5 mm Cylinder temperature: C ₁ 165 ° C., cylinder C ₂ 170
℃, C ₃ 175 ℃, cylinders C ₄ 170 ° C. Adapter Temperature: 175 ° C. Turn head temperature: 175 ° C. die temperature: 175 ° C. nozzle temperature: 175 ° C. (nozzle resin temperature of about 190 ° C.) extrusion rate: 10 kg / Time

The strand (fibers of the polyvinyl chloride resin composition) flowing out of the nozzle is introduced into a heating cylinder (250 ° C. atmosphere), is instantaneously heated and melted, and is placed at a position of about 4.5 m immediately below the nozzle. It is wound by a take-up machine.
The strand remains undrawn. At the time of this winding, the fineness (average value of 120 yarns) of the undrawn yarn is 160 to
The take-up speed was adjusted to 170 denier. Next, the undrawn yarn is passed through a first tank (under a pressurized steam atmosphere at 110 ° C.) by a two-tank drawing machine, drawn 3.5 times, and then drawn into a second tank (1).
(In an atmosphere of 10 ° C.) to relax 5.9% to give a drawn yarn. Further, the drawn yarn was relaxed 25% by a successive relaxation method in an atmosphere at 115 ° C. so that the fineness became 65 to 70 d.

At this time, the maximum draft ratio, the frequency of yarn breakage (number of times / hour), the initial coloring property, and the state of the fiber were evaluated. The results are shown in Table 2.

(Maximum draft ratio) The take-up speed is increased with respect to the speed of the yarn extruded from the nozzle, and the ratio at the time when single yarn breakage starts to occur frequently is taken. The higher the maximum draft ratio, the better the drawability and the finer the fineness.

(Yarn break frequency) Melt spinning is performed continuously for 8 hours, the number of times a single yarn breaks (several of 120 breaks) is measured, and the yarn break frequency per hour (number / hour)
And evaluated according to the following three grades. ○: None △: 1-2 times ×: 3 times or more

(Initial Colorability) The color of the yarn extruded from the nozzle was visually evaluated according to the following three grades. ：: No yellowing was observed. Δ: Slight yellowing is observed. ×: Clear yellowing is observed.

(State of Fiber) The occurrence of partial deterioration (presence or absence of carbides) in the single yarn of the yarn extruded from the nozzle was visually evaluated. ○: Available ×: Not available

[0065]

[Table 2]

As is clear from the above Examples and Comparative Examples, even when a hydrotalcite compound is used as a stabilizer, when a silicic acid compound is not used in combination, a carbide is generated in a single yarn of the yarn, and the yarn breaks. It occurs frequently (Comparative Example 2-1).
Further, when a metal soap-based stabilizer is used in place of the hydrotalcite compound, the generation of carbides can be prevented, but the spinnability and coloring properties are reduced. No (Comparative Examples 2-2 and 2-3).

On the other hand, when a hydrotalcite compound and a silicic acid compound are used in combination as a stabilizer, not only the generation of carbides can be prevented, but also the spinnability and coloring properties are improved (Example 2-1). ２−2-6). In particular, a stabilizer composition in which a hydrotalcite compound and a silicate compound are pre-mixed has excellent dispersibility in a vinyl chloride-based resin because there is no aggregation of the stabilizer component as apparent from the low bulk density. It is considered that when this stabilizer composition is used, the spinning property and the coloring property are excellent and the frequency of single yarn breakage is low as compared with the case where the stabilizer component is separately compounded. Thus, it becomes possible to produce a vinyl chloride resin fiber (Examples 2-1 to 2-5).

[0068]

Industrial Applicability The vinyl chloride fiber obtained from the vinyl chloride resin composition for fibers of the present invention has no "thread break", "burn" or "uneven color", and is suitably used as artificial hair fiber. be able to.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/07 C08K 5/07 C08L 27/06 C08L 27/06 (72) Inventor Akira Moroi Kamakura, Kanagawa Prefecture 2-13-1, Ichidai, Toyo Kagaku Co., Ltd. (72) Inventor Hidehiro Ishizuka 5-2-13, Shirahata, Urawa-shi, Saitama F-term in Asahi Denka Kogyo Co., Ltd. 4J002 BB062 BB072 BB242 BC062 BD041 BD051 BD061 BD071 BD081 BD102 BD181 BN152 CF002 DE286 DJ007 DJ017 EE049 EG048 EG058 EG078 EJ078 EW048 EW128 FD020 FD030 FD040 FD050 FD170 FD200 GK01 4L035 BB21 BB80 BB89 BB91 FF04 HK08 JJ08 JJ08 KK08

Claims (8)

[Claims] [Claim 1] 100 parts by weight of a vinyl chloride resin,
(A) at least one hydrotalcite compound;
A vinyl chloride resin composition for fibers, comprising from 0.01 to 10 parts by weight and at least 0.001 to 1 part by weight of a (b) silicate compound. 2. The vinyl chloride resin composition for fibers according to claim 1, wherein the silicate compound of the component (b) is silicon dioxide. 3. The composition according to claim 1, further comprising at least one zinc salt of an organic acid, wherein the content is 0.01 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin. Or the vinyl chloride resin composition for fibers according to 2. 4. The method according to claim 1, further comprising at least one kind of β-diketone, wherein the content is 0.01 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin. 4. The vinyl chloride resin composition for fibers according to 2 or 3. (5) Hydrotalcite compound 100
A stabilizer composition for a vinyl chloride resin for fibers, comprising 0.1 to 50 parts by weight of a (b) silicate compound based on parts by weight. 6. The stabilizer composition for a vinyl chloride resin for fibers according to claim 5, wherein the silicate compound of the component (b) is silicon dioxide. 7. The composition further comprises at least one zinc salt of an organic acid, the content of which is 0.1 to 50 parts by weight based on 100 parts by weight of the hydrotalcite compound (a). The stabilizer composition for a vinyl chloride resin for fibers according to claim 5 or 6. 8. The method according to claim 1, further comprising at least one kind of β-diketone, wherein the content is 0.1 to 50 parts by weight based on 100 parts by weight of the hydrotalcite compound (a). Item 8. The stabilizer composition for a vinyl chloride resin for fibers according to Item 5, 6 or 7.