JP2005068576A - Flame retardant polyester fiber for artificial hair - Google Patents

Abstract

PROBLEM TO BE SOLVED: To maintain a fiber property such as heat resistance and strong elongation of a normal polyester fiber, excellent in flame retardancy, setability, combing property, and controlled the gloss of the fiber, and a polyester artificial hair fiber using the same Provide artificial hair.
SOLUTION: A composition obtained by melt-kneading a polyester containing a phosphorus-containing flame retardant and / or a bromine-containing flame retardant and an additive comprising at least one of a compatibilizer, a lubricant and a bleed inhibitor, or polyester and phosphorus The above-mentioned problems have been solved by melt spinning a composition obtained by melt-kneading a copolymer obtained by copolymerizing a contained flame retardant and an additive comprising at least one of a compatibilizer, a lubricant and a bleed inhibitor. A flame-retardant polyester-based artificial hair fiber is obtained.
[Selection figure] None

Description

  The present invention provides a composition obtained by melt-kneading a polyester containing a phosphorus-containing flame retardant and / or bromine-containing flame retardant and an additive comprising at least one of a compatibilizer, a lubricant and a bleed inhibitor, or a polyester and phosphorus Flame retardant polyester artificial hair formed from a copolymer obtained by copolymerizing a flame retardant containing and a composition obtained by melt-kneading an additive comprising at least one of a compatibilizer, a lubricant and a bleed inhibitor Relating to textiles. More specifically, the present invention relates to a fiber for artificial hair that maintains fiber properties such as flame retardancy, heat resistance, and high elongation, and is excellent in setability and drip resistance.

  Fibers made of polyethylene terephthalate or polyester mainly composed of polyethylene terephthalate have high melting point, high elastic modulus and excellent heat resistance and chemical resistance, so curtains, rugs, clothing, blankets, sheets, and tables Widely used for cloth, chair upholstery, wall covering, artificial hair, automotive interior materials, outdoor reinforcement, safety nets, etc.

  On the other hand, human hair, artificial hair (modacrylic fiber, polyvinyl chloride fiber) and the like have been used in hair products such as wigs, hair wigs, furs, hair bands, doll hairs. However, provision of human hair has become difficult, and the importance of artificial hair has increased.

  As an artificial hair material, modacrylic fiber has been frequently used taking advantage of flame retardancy, but it is insufficient in terms of heat resistance. In recent years, artificial hair using fibers mainly composed of polyester typified by polyethylene terephthalate having excellent heat resistance has been proposed. However, since the fiber from the polyester represented by polyethylene terephthalate is a combustible material, the flame resistance is insufficient.

  Conventionally, various attempts have been made to improve the flame resistance of polyester fibers. For example, a method of forming fibers from polyester obtained by copolymerizing a flame retardant monomer containing a phosphorus atom, and a flame retardant for polyester fibers. The method of making it contain is known.

  Examples of the method of copolymerizing the former flame-retardant monomer include a method of copolymerizing a phosphorus compound having a phosphorus atom as a ring member and good thermal stability (Patent Document 1), and carboxyphosphinic acid. There are proposed a method of copolymerizing (Patent Document 2), a method of blending or copolymerizing a phosphorus compound with a polyester containing polyarylate (Patent Document 3), and the like. For example, a polyester fiber obtained by copolymerizing a phosphorus compound has been proposed as an application of the flame retarding technique to artificial hair (Patent Documents 4 and 5). However, since artificial hair is required to have high flame resistance, in order to use these copolymerized polyester fibers for artificial hair, the amount of copolymerization must be increased. As a result, the heat resistance of polyester is reduced. When the temperature is greatly reduced and melt spinning becomes difficult or the flame approaches, there is another problem that it does not ignite and burn but melts and drip.

  On the other hand, as a method of containing the latter flame retardant, there are a method of containing a fine halogenated cycloalkane compound in a polyester fiber (Patent Document 6), a method of containing a bromine atom-containing alkylcyclohexane (Patent Document 7), and the like. Proposed. In the method of adding a flame retardant to the polyester fiber, in order to obtain sufficient flame resistance, it is necessary to increase the content treatment temperature to 150 ° C. or higher or to increase the content treatment time. Or a large amount of a flame retardant has to be used, causing problems such as a decrease in fiber properties, a decrease in productivity, and an increase in manufacturing costs.

Thus, the actual condition is that an artificial hair that maintains the fiber properties such as flame retardancy, heat resistance, and high elongation of conventional polyester fibers and is excellent in setability and combing properties has not yet been obtained.
Japanese Patent Publication No. 55-41610 Japanese Patent Publication No.53-13479 Japanese Patent Laid-Open No. 11-124732 JP-A-3-27105 JP-A-5-339805 Japanese Patent Publication No. 3-57990 Japanese Patent Publication No. 1-2913

  The present invention solves the conventional problems as described above, maintains the fiber physical properties such as heat resistance and high elongation of ordinary polyester fiber, is excellent in flame retardancy, setability, drip resistance, combing, An object of the present invention is to provide a flame-retardant polyester artificial hair fiber in which the gloss of the fiber is controlled.

  As a result of intensive investigations to solve the above problems, the present inventors have added to the polyester one or more of a phosphorus-containing flame retardant and / or a bromine-containing flame retardant and a compatibilizer, a lubricant, and a bleed inhibitor. A composition obtained by melt-kneading an agent, or a melt-kneaded additive comprising at least one of a copolymer obtained by copolymerizing a polyester and a phosphorus-containing flame retardant, a compatibilizer, a lubricant, and a bleed inhibitor. By melt-spinning the resulting composition, the fiber properties such as heat resistance and high elongation of ordinary polyester fiber are maintained, and flame retardancy, setability, transparency, color developability, tactile sensation, and excellent resistance to combing. It has been found that fibers for flammable polyester-based artificial hair can be obtained, and by mixing organic fine particles and / or inorganic fine particles into the composition, the gloss of the fibers can be controlled without causing deterioration of the physical properties of the fibers. It found that it is possible to roll, which resulted in the completion of the present invention.

  That is, the present invention relates to a phosphorus-containing flame retardant and / or a bromine-containing flame retardant (B) with respect to 100 parts by weight of a polyester (A) comprising at least one of polyalkylene terephthalate and a copolymer polyester mainly composed of polyalkylene terephthalate. A composition obtained by melt-kneading 3 to 30 parts by weight and 0.1 to 20 parts by weight of an additive (C) comprising at least one of a compatibilizer, a lubricant and a bleed inhibitor, or the component (A) 1 part of a compatibilizer, a lubricant and a bleed inhibitor with respect to 100 parts by weight of a copolymer (D) obtained by copolymerizing 2 to 10 parts by weight of a reactive phosphorus-based flame retardant which is a component (B) that can be copolymerized with It is a flame-retardant polyester-based artificial hair fiber formed from a composition obtained by melt-kneading 0.1 to 20 parts by weight of additive (C) comprising at least seeds, preferably component (A) The above-mentioned flame retardant polyester-based artificial hair fiber, which is at least one polymer selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate, component (B) is a phosphate compound, phosphonate compound, phosphinate Compound, phosphine oxide compound, phosphonite compound, phosphinite compound, phosphine compound and condensed phosphate ester compound, and / or bromine-containing phosphate ester flame retardant, bromine Polystyrene flame retardant, brominated benzyl acrylate flame retardant, brominated polycarbonate flame retardant, tetrabromobisphenol A derivative, bromine-containing triazine compound, bromine-containing isocyanuric acid The above-mentioned flame-retardant polyester-based artificial hair fiber, which is at least one flame retardant selected from the group consisting of a product, component (C) is an ethylene-glycidyl (meth) acrylate copolymer, ethylene-maleic anhydride copolymer Polymer, ethylene-ethyl (meth) acrylate-maleic anhydride copolymer, ethylene-methyl (meth) acrylate copolymer, ethylene-glycidyl (meth) acrylate copolymer-g-polystyrene, ethylene-glycidyl (meth) Acrylate copolymer-g-polymethyl methacrylate, ethylene-glycidyl (meth) acrylate copolymer-g-acrylonitrile-styrene copolymer, ethylene-ethyl (meth) acrylate-maleic anhydride copolymer-g-polystyrene, Ethylene-ethyl (meth) acrylate-maleic anhydride Acid copolymer-g-polymethyl methacrylate, ethylene-ethyl (meth) acrylate-maleic anhydride copolymer-g-acrylonitrile-styrene copolymer, montanic acid wax, montanic acid ester wax, partially saponified montan 9. An additive comprising at least one of acid wax, metal montanate, polyethylene wax, oxidized polyethylene wax, polytetrafluoroethylene, fluorine-modified wax, polydimethyl silicone, and modified silicone resin. The flame retardant polyester-based artificial hair fiber according to any one of the above.

  Further, the composition comprising the components (A), (B), and (C) or the composition comprising the components (C) and (D), from an antimony trioxide compound, an antimony pentoxide compound, and sodium antimonate The above-mentioned flame retardant polyester-based artificial hair fiber mixed with at least one selected from the group consisting of flame retardant aid (E), and organic fine particles (F) and / or inorganic fine particles (G) And (F) component is at least one selected from the group consisting of polyarylate, polyamide, fluororesin, silicon resin, cross-linked acrylic resin, and cross-linked polystyrene. , (G) component is calcium carbonate, silicon oxide, titanium oxide, aluminum oxide, zinc oxide, talc, kaolin, montmorillonite, bentonite, The present invention relates to the above-mentioned flame retardant polyester artificial hair fiber, which is at least one selected from the group consisting of mica.

  The flame-retardant polyester-based artificial hair fibers are preferably non-crimped raw yarns and are attached to the fiber, and the single fiber fineness is preferably 30 to 80 dtex.

  According to the present invention, a polyester fiber that maintains the physical properties of ordinary polyester fibers such as heat resistance and high elongation, is excellent in flame retardancy, setability and combing properties, and has a controlled fiber gloss, and the same are used. Artificial hair is obtained.

  The fiber for flame retardant polyester-based artificial hair of the present invention is a polyester (A) comprising at least one of polyalkylene terephthalate and a copolymerized polyester mainly composed of polyalkylene terephthalate, a phosphorus-containing flame retardant and / or a bromine-containing flame retardant. (B) and a composition obtained by melt-kneading an additive (C) comprising at least one of a compatibilizer, a lubricant and an anti-bleed agent, or a polyester (A) and a phosphorus-containing flame retardant (B). A fiber obtained by melt spinning a composition obtained by melt-kneading a copolymer (D) copolymerized with an additive (C) comprising at least one of a compatibilizing agent, a lubricant and an anti-bleeding agent.

  Examples of the polyalkylene terephthalate contained in the polyester (A) used in the present invention or a copolymer polyester mainly composed of polyalkylene terephthalate include polyalkylene terephthalates such as polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate and / or their Examples thereof include a copolymer polyester mainly composed of alkylene terephthalate and containing a small amount of a copolymer component.

  The main component means containing 80 mol% or more.

  Examples of the copolymer component include isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, trimellitic acid, pyromellitic acid, succinic acid, glutaric acid, adipic acid, superic acid, azelaic acid, sebacic acid , Polycarboxylic acids such as dodecanedioic acid, derivatives thereof, dicarboxylic acids including sulfonates such as 5-sodium sulfoisophthalic acid, dihydroxyethyl 5-sodium sulfoisophthalate, derivatives thereof, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, polyethylene glycol, trimethylolpropane, pentaerythritol, 4-hydro Shi benzoic acid, etc. ε- caprolactone.

  The copolymer polyester is usually produced by reacting a main component of terephthalic acid and / or a derivative thereof (for example, methyl terephthalate) and a polymer of alkylene glycol with a small amount of a copolymer component. Although it is preferable from the viewpoint of stability and ease of operation, a monomer or oligomer which is a small amount of a copolymer component in a mixture of terephthalic acid and / or its derivative (for example, methyl terephthalate) as a main component and alkylene glycol You may manufacture by polymerizing what contained the component.

  The copolymerized polyester is not particularly limited as long as the copolymerized component is polycondensed to the main chain and / or side chain of the main polyalkylene terephthalate.

  Specific examples of the copolymer polyester mainly composed of the polyalkylene terephthalate include, for example, a polyester mainly composed of polyethylene terephthalate and copolymerized with ethylene glycol ether of bisphenol A, a polyester copolymerized with 1,4-cyclohexanedimethanol, 5 -Polyester copolymerized with dihydroxyethyl sodium sulfoisophthalate.

  The polyalkylene terephthalate and the copolyester may be used singly or in combination of two or more. Among these, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, copolymerized polyester (polyester mainly composed of polyethylene terephthalate and copolymerized with ethylene glycol ether of bisphenol A, polyester copolymerized with 1,4-cyclohexanedimethanol, Polyester copolymerized with dihydroxyethyl 5-sodiumsulfoisophthalate) is preferred, and those in which two or more of these are mixed are also preferred.

  The intrinsic viscosity of component (A) is preferably 0.5 to 1.4, more preferably 0.6 to 1.2. If the intrinsic viscosity is less than 0.5, the mechanical strength of the resulting fiber tends to decrease, and if it exceeds 1.4, the melt viscosity increases with increasing molecular weight, making melt spinning difficult, There is a tendency for the fineness to be non-uniform.

  There is no limitation in particular in the phosphorus containing flame retardant (B) used for this invention, If it is a phosphorus containing flame retardant generally used, it can be used. Here, the phosphorus-containing flame retardant (B) may be used by mixing a non-copolymerized phosphorus-containing flame retardant with other components, or by copolymerizing a reactive phosphorus-containing flame retardant with the component (A). (D) component may be used.

  As the non-copolymerization type component (B), phosphate compounds, phosphonate compounds, phosphinate compounds, phosphine oxide compounds, phosphonite compounds, phosphinite compounds, phosphine compounds, for example, the general formula (1):

(In the formula, R ¹ is a monovalent aromatic hydrocarbon group or aliphatic hydrocarbon group, and they may be the same or different. R ² is a divalent aromatic hydrocarbon group. And when two or more are included, they may be the same or different. N represents 0 to 15.)
The condensed phosphate ester type compound represented by these is mention | raise | lifted. These may be used alone or in combination of two or more. Among these, a condensed phosphate ester compound represented by the general formula (2) is preferable.

  Specific examples of the non-copolymerized phosphorus-containing flame retardant (B) include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (Isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinephtyl phosphate, cresylphenyl phosphate, xylenyl diphenyl phosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, etc. Resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A poly Checkout Le phosphate, and the like hydroquinone poly (2,6-xylyl) phosphate, wherein:

And a condensed phosphate ester compound represented by the general formula (2) including the compound represented by formula (2).

  Moreover, as a reactive type (B) component used when obtaining (D) component, the reactive phosphorus flame retardant copolymerizable with (A) component can be used, and general formula (2)-( 7):

Wherein R ³ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, R ⁴ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, m Represents an integer of 1 to 11.)

(In the formula, R ⁵ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different.)

(In the formula, R ⁶ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ⁷ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. And they may be the same or different, and l represents an integer of 1 to 12.)

(In the formula, R ⁸ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ⁹ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. These may be the same or different, and p represents an integer of 1 to 11.)

(In the formula, R ¹⁰ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different. Y is a hydrogen atom, a methyl group or 6 carbon atoms. -12 aromatic hydrocarbon groups, r and s each represent an integer of 1 to 20)

(In the formula, R ¹¹ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ¹² is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. And they may be the same or different, and t represents an integer of 1 to 20.)
Specific examples include, for example, diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-methacryloyloxy, and the like. Ethyl phosphate, tris (3-hydroxypropyl) phosphine, tris (4-hydroxybutyl) phosphine, tris (3-hydroxypropyl) phosphine oxide, tris (3-hydroxybutyl) phosphine oxide, 3- (hydroxyphenylphosphinoyl) Propionic acid and the formula:

And phosphorus-containing compounds such as

  The amount of the reactive phosphorus flame retardant used is in the range of 2 to 10 parts by weight, more preferably 3 to 9 parts by weight, and still more preferably 4 to 8 parts by weight with respect to 100 parts by weight of the component (A). . If the amount used is less than 2% by weight, it is difficult to obtain a flame retardant effect. In obtaining the component (D), a known method can be used for the production of the thermoplastic copolymer polyester copolymerized with the reactive phosphorus-based flame retardant. The dicarboxylic acid, its derivative, the diol component, its derivative, and the reactive type can be used. A method of mixing and polycondensing a phosphorus-based flame retardant, or depolymerizing a thermoplastic polyester using a diol component such as ethylene glycol, mixing a reactive phosphorus-based flame retardant at the time of depolymerization, and again polycondensing to co-polymerize A method for obtaining a coalescence is preferable.

  The bromine-containing flame retardant (B) used in the present invention is not particularly limited, and any bromine-containing flame retardant generally used can be used.

  Specific examples of the component (B) include pentabromotoluene, hexabromobenzene, decabromodiphenyl, decabromodiphenyl ether, bis (tribromophenoxy) ethane, tetrabromophthalic anhydride, ethylenebis (tetrabromophthalimide), ethylenebis ( Represented by bromine-containing phosphates such as pentabromophenyl), octabromotrimethylphenylindane, tris (tribromoneopentyl) phosphate, brominated polystyrenes represented by general formula (8), and general formula (9) Brominated polybenzyl acrylates, brominated epoxy oligomers represented by general formula (10), brominated polycarbonate oligomers represented by general formula (11), tetrabromobisphenol A, tetrabromobisphenol A-bis ( 2, 3 Dibromopropyl ether), tetrabromobisphenol A-bis (allyl ether), tetrabromobisphenol A-bis (hydroxyethyl ether), tetrabromobisphenol A derivatives represented by general formula (12), tris (tribromophenoxy) triazine Bromine-containing triazine-based compounds such as, bromine-containing isocyanuric acid-based compounds such as tris (2,3-dibromopropyl) isocyanurate, and the like. These may be used alone or in combination of two or more.

(In the formula, X represents 1 to 5, and a represents 5 to 200.)
Brominated polystyrene having a structure represented by

(In formula, b shows 5-100.)
Brominated polyacrylates having a structure represented by

(Wherein c represents 5 to 200)

(In the formula, R ¹³ is a hydrogen atom or a bromine atom, and they may be the same or different from each other. D represents 1 to 80.)

(In the formula, R ¹⁴ is a hydrogen atom or a bromine atom, and they may be the same or different. E represents 1 to 80.)
Among these, bromine-containing phosphate ester flame retardant, brominated polystyrene flame retardant, brominated benzyl acrylate flame retardant, brominated epoxy flame retardant, brominated polycarbonate flame retardant, tetrabromobisphenol A derivative, bromine Preferred are triazine compounds containing bromine and isocyanuric acid compounds containing bromine.

  The amount of the component (B) used is preferably 3 to 30 parts by weight, more preferably 3 to 25 parts by weight, and still more preferably 4 to 20 parts by weight with respect to 100 parts by weight of the component (A). When the amount used is less than 2 parts by weight, it becomes difficult to obtain a flame retardant effect, and when it is more than 30 parts by weight, mechanical properties, heat resistance, and drip resistance are impaired.

  There is no particular limitation on the additive (C) comprising at least one of a compatibilizer, a lubricant and a bleed inhibitor used in the present invention, and any commonly used additive can be used.

  Specific examples of the component (C) include, for example, an ethylene-glycidyl (meth) acrylate copolymer, an ethylene-ethyl (meth) acrylate copolymer, an ethylene-maleic anhydride copolymer, and an ethylene-ethyl (meth) acrylate. -Maleic anhydride copolymer, ethylene-methyl (meth) acrylate copolymer, ethylene-vinyl acetate copolymer, acrylonitrile-styrene copolymer, polyethylene-g-polystyrene, polyethylene-g-polymethylmethacrylate, polyethylene- g-acrylonitrile-styrene copolymer, propylene-g-styrene, propylene-g-acrylonitrile-styrene copolymer, ethylene-glycidyl (meth) acrylate copolymer-g-polystyrene, ethylene-glycidyl (meth) acrylate copolymer Coalescence g-polymethyl methacrylate, ethylene-glycidyl (meth) acrylate copolymer-g-acrylonitrile-styrene copolymer, ethylene-ethyl (meth) acrylate copolymer-g-polystyrene, ethylene-ethyl (meth) acrylate copolymer Compound-g-polymethyl methacrylate, ethylene-ethyl (meth) acrylate copolymer-g-acrylonitrile-styrene copolymer, ethylene-vinyl acetate copolymer-g-polystyrene, ethylene-vinyl acetate copolymer-g- Polymethyl methacrylate, ethylene-vinyl acetate copolymer-g-acrylonitrile-styrene copolymer, ethylene-ethyl (meth) acrylate-maleic anhydride copolymer-g-polystyrene, ethylene-ethyl (meth) acrylate-maleic anhydride Acid copolymer g-polymethyl methacrylate, ethylene-ethyl (meth) acrylate-maleic anhydride copolymer-g-acrylonitrile-styrene copolymer, montanic acid wax, montanic acid ester wax, partially saponified montanic acid wax, montan Acid metal salt, hydrocarbon wax, ethylene-vinyl acetate copolymer wax, ethylene oxide-vinyl acetate copolymer wax, polyethylene wax, polyethylene oxide wax, polypropylene wax, amide wax, amide modified wax, polytetrafluoro Examples thereof include ethylene, fluorine-modified wax, fatty acid ester, glycerin ester, sorbitan ester, fatty acid amide, aliphatic polyester, polydimethyl silicone, and modified silicone resin.

  Among these, ethylene-glycidyl (meth) acrylate copolymer, ethylene-maleic anhydride copolymer, ethylene-ethyl (meth) acrylate-maleic anhydride copolymer, ethylene-methyl (meth) acrylate copolymer , Ethylene-glycidyl (meth) acrylate copolymer-g-polystyrene, ethylene-glycidyl (meth) acrylate copolymer-g-polymethyl methacrylate, ethylene-glycidyl (meth) acrylate copolymer-g-acrylonitrile-styrene copolymer Polymer, ethylene-ethyl (meth) acrylate-maleic anhydride copolymer-g-polystyrene, ethylene-ethyl (meth) acrylate-maleic anhydride copolymer-g-polymethyl methacrylate, ethylene-ethyl (meth) acrylate -Anhydrous male Acid copolymer-g-acrylonitrile-styrene copolymer, montanic acid wax, montanic acid ester wax, partially saponified montanic acid wax, montanic acid metal salt, polyethylene wax, polyethylene oxide wax, polytetrafluoro Ethylene, fluorine-modified wax, polydimethyl silicone, and modified silicone resin are preferred.

  The amount of the component (C) used is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 15 parts by weight, and further 0.3 to 10 parts by weight with respect to 100 parts by weight of the component (A). preferable. If the amount used is less than 0.1 parts by weight, the effects of compatibilization, bleed suppression, and fiber surface smoothing will not be exhibited. If the amount used exceeds 20 parts by weight, mechanical properties, heat resistance, flame resistance, and drip resistance will be exhibited. Damaged.

  In the present invention, by using the component (C), the compatibility or dispersion state of the component (A) and the component (B) is improved, so that bleeding out of the component (B) to the fiber surface is suppressed. In addition, there is no stickiness on the fiber surface, and furthermore, slipperiness can be imparted and a filament with good comb characteristics can be obtained. Even when the component (D) is used, the effect of the component (C) exhibits effects other than compatibility and dispersion, so that there is no stickiness on the fiber surface and it is possible to impart slipperiness. This is the same in that a good comb filament can be obtained.

  The flame retardant polyester-based composition used in the present invention is, for example, various kinds of general components after dry blending the components (A), (B) and (C), or the components (C) and (D). It can manufacture by melt-kneading using a kneader.

  Examples of the kneader include a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, and a kneader. Among these, a twin screw extruder is preferable from the viewpoint of adjusting the degree of kneading and ease of operation.

  In order to improve the flame retardant effect, the flame retardant polyester-based artificial hair fiber of the present invention exhibits flame retardancy by blending the component (B) or using the component (D) ( E) A component can be mix | blended.

  The antimony flame retardant aid (E) used in the present invention is not particularly limited, and specific examples include an antimony trioxide compound, an antimony pentoxide compound, and sodium antimonate.

  The particle size of the component (E) is not particularly limited, but is preferably 0.02 to 5 μm, more preferably 0.02 to 3 μm, and further preferably 0.02 to 2 μm. Moreover, you may surface-treat with an epoxy compound, a silane compound, an isocyanate compound, a titanate compound etc. as needed. (E) The usage-amount of a component has preferable 0-5 weight part with respect to 100 weight part of (A) component, 0-3 weight part is more preferable, 0-2 weight part is further more preferable. When the amount used is more than 5 parts by weight, appearance, hue and color developability are impaired.

  The fiber for flame retardant polyester-based artificial hair of the present invention is mixed with organic fine particles (F) and / or inorganic fine particles (G) to form fine protrusions on the fiber surface to adjust the gloss and gloss of the fiber surface. can do.

  The component (F) can be used as long as it is an organic resin component having a structure that is not compatible with or partially compatible with the main component (A) and / or (B). , Polyarylate, polyamide, fluororesin, silicone resin, crosslinked acrylic resin, crosslinked polystyrene, and the like. These may be used alone or in combination of two or more.

  As the component (G), those having a refractive index close to the refractive index of the component (A) and / or the component (B) are preferable from the viewpoint of the effects on the transparency and color developability of the fiber, such as calcium carbonate, silicon oxide, Examples thereof include titanium oxide, aluminum oxide, zinc oxide, talc, kaolin, montmorillonite, bentonite, and mica.

  The fiber for flame-retardant polyester-based artificial hair of the present invention can be produced by melt spinning the flame-retardant polyester-based composition by an ordinary melt spinning method.

  That is, for example, the temperature of an extruder, a gear pump, a die, etc. is set to 270 to 310 ° C., melt-spun, the spun yarn is passed through a heating tube, cooled to the glass transition point or lower, and 50 to 5000 m / min. A spun yarn is obtained by pulling at a speed of. It is also possible to control the fineness by cooling the spun yarn in a water tank containing cooling water. The temperature and length of the heating cylinder, the temperature and blowing amount of the cooling air, the temperature of the cooling water tank, the cooling time, and the take-up speed can be appropriately adjusted depending on the discharge amount and the number of holes in the die.

  The obtained spun yarn is heat-drawn, and the drawing is performed by any one of a two-step method in which the spun yarn is once wound and then drawn and a direct spin-drawing method in which the drawn yarn is continuously drawn without being wound. Also good. The hot stretching is performed by a one-stage stretching method or a multi-stage stretching method having two or more stages. As a heating means in the heat stretching, a heating roller, a heat plate, a steam jet device, a hot water tank, or the like can be used, and these can be used in combination as appropriate.

  In the flame-retardant polyester-based artificial hair fiber of the present invention, if necessary, a flame retardant other than the component (B), a heat-resistant agent, a light stabilizer, a fluorescent agent, an antioxidant, an antistatic agent, a pigment, Various additives such as a plasticizer and a lubricant can be contained. By incorporating a pigment, a primary fiber can be obtained.

  The flame retardant polyester-based artificial hair fiber of the present invention thus obtained is a non-crimped raw fiber-like fiber, and its fineness is usually 30 to 80 dtex, more preferably 35 to 75 dtex. Suitable for artificial hair. In addition, the artificial hair fiber has heat resistance capable of using a beauty heat instrument (hair iron) at 160 to 200 ° C., is difficult to ignite, and preferably has self-extinguishing properties.

  When the flame-retardant polyester fiber of the present invention is attached, it can be used as it is, but when it is not attached, it can be dyed under the same conditions as a normal flame-retardant polyester fiber. .

  As pigments, dyes, auxiliaries and the like used for dyeing, those having good weather resistance and flame retardancy are preferable.

  The fiber for flame-retardant polyester-based artificial hair of the present invention is excellent in curl setting using a beauty heat instrument (hair iron) and excellent in curl retention. Further, the surface of the fiber is appropriately matted due to the unevenness of the fiber surface, and can be used as artificial hair. Furthermore, using oil agents, such as a fiber surface treating agent and a softening agent, a touch feeling and a feeling can be provided, and it can be made closer to human hair.

  Moreover, the fiber for flame-retardant polyester-based artificial hair of the present invention may be used in combination with other artificial hair materials such as modacrylic fiber, polyvinyl chloride fiber, and nylon fiber, or in combination with human hair.

  Human hair used in hair products such as wigs, hair wigs, and false hairs is generally treated with a cuticle, decolored and dyed, and a silicone fiber surface treatment agent, Because it uses a softening agent, it is flammable unlike untreated human hair, but the fiber for flame-retardant polyester-based artificial hair of the present invention and human hair were mixed at a human hair mixing ratio of 60% or less. Show good flame retardancy.

  Next, the present invention will be described more specifically based on examples, but the present invention is not limited thereto.

The characteristic value measurement method is as follows.
(Strength and elongation)
The tensile strength / elongation of the filament is measured using INTESCO Model 201 manufactured by Intesco. A filament having a length of 40 mm is taken, 10 mm on both ends of the filament is sandwiched with a backing (thin paper) to which a double-sided tape with glue is attached, and air-dried overnight to prepare a sample having a length of 20 mm. A sample is mounted on a testing machine, a test is performed at a temperature of 24 ° C., a humidity of 80% or less, a load of 1/30 gF × fineness (denier), and a tensile speed of 20 mm / min to measure the strength and elongation. The test is repeated 10 times under the same conditions, and the average value is defined as the filament elongation.
(Flame retardance)
A filament with a fineness of about 50 dtex is cut to a length of 150 mm, 0.7 g is bundled, one end is clamped and fixed to a stand, and then suspended vertically. A 20 mm flame is indirectly flamed for 3 seconds on a fixed filament having an effective length of 120 mm and burned. The flammability is ◎ when the afterflame time is 0 second (not ignited), ○ when less than 3 seconds, △ 3-10 when △, 10 seconds or more when ×, and drip resistance when the drip number is 0 Evaluation is based on 5 or less as ◯, 6 to 10 as Δ, and 11 or more as ×.
(Glossy)
A tow filament having a length of 30 cm and a total fineness of 100,000 dtex is visually evaluated under sunlight.

◎: Gloss is adjusted to a level equivalent to human hair ○: Gloss is adjusted moderately △: Slightly too glossy or slightly glossy ×: Too much gloss or gloss Too little (feel)
A tow filament having a length of 30 cm and a total fineness of 100,000 dtex is touched by hand to evaluate the sticky feeling on the filament surface.

○: No sticky feeling △: Some sticky feeling ×: Sticky feeling (comb street)
Soaked in a 3% aqueous solution containing a PO / EO random copolymer (molecular weight 20000) and a cationic antistatic agent at a ratio of 50/50 as a fiber surface treatment agent in a tow filament having a length of 30 cm and a total fineness of 100,000 dtex Each is 0.1% attached and dried at 80 ° C. for 5 minutes. A comb (made by Delrin resin) is passed through the treated tow filament, and the ease of passing the comb is evaluated.

○: Almost no resistance (light)
Δ: Some resistance (heavy)
×: There is considerable resistance, or it is caught in the middle (iron set property)
It is an index of the ease of curling with a hair iron and the retention of the curled shape. The filament is clamped between hair irons heated to 180 ° C. and preheated by handling 3 times. At this time, fusion between filaments, combing, filament shrinkage, and thread breakage are visually evaluated. Next, the preheated filament is beaten on a hair iron, held for 10 seconds, and the iron is pulled out. The ease of pulling out (rod-out property) at this time and the curl retaining property when pulled out are visually evaluated.
(Examples 1-17)
Polyester terephthalate for coloring PESM6100 BLACK in the composition shown in Tables 1 and 2 consisting of polyethylene terephthalate, brominated epoxy flame retardant, antimony flame retardant aid, organic fine particles and inorganic fine particles dried to a water content of 100 ppm or less 2 parts (made by Dainichi Seika Kogyo Co., Ltd., carbon black content 30%, polyester is included in component (A)), dry blended, supplied to twin screw extruder, melt kneaded at 280 ° C And pelletized, and then dried to a moisture content of 100 ppm or less. Next, using a melt spinning machine, the molten polymer is discharged from a spinneret having a round cross-section nozzle hole with a nozzle diameter of 0.5 mm at 280 ° C., and cooled in a water bath at a water temperature of 50 ° C. set at a position 30 mm below the base. The undrawn yarn was obtained by winding at a speed of 100 m / min. The obtained unstretched yarn is stretched in a warm water bath at 80 ° C. to obtain a 4-fold stretched yarn, wound at a speed of 100 m / min using a heat roll heated to 200 ° C., heat treated, and single fiber A polyester fiber (multifilament) having a fineness of about 50 dtex was obtained.

* 1: Polyethylene terephthalate, manufactured by Nippon Unipet Co., Ltd. * 2: 1,3-phenylenebis (dixylenyl phosphate), manufactured by Daihachi Chemical Industry Co., Ltd. * 3: Tris (tribromoneopentyl) phosphate, large * 4: Brominated epoxy flame retardant, manufactured by Toto Kasei Co., Ltd. * 5: Ethylene-glycidyl methacrylate copolymer, Sumitomo Chemical Co., Ltd. * 6: Ethylene-glycidyl methacrylate copolymer -G-polymethylmethacrylate polyallate, manufactured by Nippon Oil & Fats Co., Ltd. * 7: Montanate ester wax, Clariant Japan Co., Ltd.
* 8: Silicone masterbatch (silicone / polybutylene terephthalate = 50/50), Toray Dow Corning Silicone * 9: Flame retardant copolyester, manufactured by Toyobo Co., Ltd. * 10: Polyarylate, Unitika Ltd. * 11: Talc, manufactured by Fuji Talc Co., Ltd. * 12: Silica, manufactured by UNIMIN Co., Ltd. Using the fibers obtained, high elongation, flame retardancy, gloss, touch, combing, cold setting, curl retention Tables 3 and 4 show the results of evaluating the iron setting properties.

(Comparative Example 1)
10 parts by weight of 1,3-phenylenebis (dixylenyl phosphate) and 1 part by weight of titanium oxide with respect to 100 parts by weight of polyethylene terephthalate (BK-2180EFG-10, manufactured by Nippon Unipet Co., Ltd.) dried to a water content of 100 ppm or less Part, 2 parts by weight of polyester pellets for coloring PESM6100 BLACK (manufactured by Dainichi Seika Kogyo Co., Ltd., carbon black content 30%), dry blended, and spinneret having a round cross-section nozzle hole with a nozzle diameter of 0.5 mm The melted polymer was discharged using, cooled in a water bath at a water temperature of 30 ° C. installed at a position 25 cm below the die, and wound at a speed of 100 m / min to obtain an undrawn yarn. The obtained undrawn yarn is drawn in a warm water bath at 80 ° C. to form a 4-fold drawn yarn, wound using a heat roll heated to 200 ° C. at a speed of 100 m / min, heat treated, and single fiber A polyester fiber (multifilament) having a fineness of 49 dtex was obtained.

(Comparative Example 2)
Flame retardant copolyester dried to a moisture content of 100 ppm or less (Heim RH416, manufactured by Toyobo Co., Ltd.) 100 parts by weight polyester pellets for coloring PESM6100 BLACK (produced by Dainichi Seika Kogyo Co., Ltd., carbon black content 30%) 2 A weight part was added and it carried out similarly to the comparative example 1, and obtained the polyester-type fiber (multifilament) whose single fiber fineness is 47 dtex.

(Comparative Example 3)
Tris (tribromoneopentyl) phosphate (CR-900, Daihachi Chemical Industry Co., Ltd.) with respect to 100 parts by weight of polyethylene terephthalate (BK-2180EFG-10, manufactured by Nihon Unipet Co., Ltd.) dried to a water content of 100 ppm or less 10 parts by weight, polyester pellets for coloring PESM6100 BLACK (manufactured by Dainichi Seika Kogyo Co., Ltd., carbon black content 30%) are added in the same manner as in Comparative Example 1, and the polyester with a single fiber fineness of 48 dtex is added. A system fiber (multifilament) was obtained.
Table 4 shows the results of evaluating the strength, flame retardancy, gloss, touch, comb, curl retention, and iron setability using the obtained fibers.

  As shown in Tables 3 and 4, it was confirmed that, in comparison with the comparative examples, the examples were excellent in flame retardancy, gloss, touch, combing, iron setability and the like. Therefore, the fiber for artificial hair using the compatibilizer, lubricant and anti-bleeding agent of this time is glossy, tactile, and set, while maintaining the mechanical and thermal properties of polyester compared to the conventional artificial hair fiber. It has been confirmed that it can be effectively used as artificial hair with improved combing.

Claims (15)

  3 to 30 parts by weight of a phosphorus-containing flame retardant and / or a bromine-containing flame retardant (B) with respect to 100 parts by weight of a polyester (A) comprising at least one polyalkylene terephthalate or a copolyester based on polyalkylene terephthalate, And for flame-retardant polyester-based artificial hair formed from a composition obtained by melt-kneading 0.1 to 20 parts by weight of additive (C) consisting of at least one of a compatibilizer, a lubricant and an anti-bleeding agent fiber.   Compatibilizer, lubricant and bleed for 100 parts by weight of copolymer (D) obtained by copolymerizing 2 to 10 parts by weight of reactive phosphorus flame retardant (B) which is copolymerizable with component (A) Flame retardant polyester-based artificial hair fibers formed from a composition obtained by melt-kneading 0.1 to 20 parts by weight of additive (C) comprising at least one inhibitor.   The flame retardant polyester-based artificial hair fiber according to claim 1 or 2, wherein the component (A) is at least one polymer selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate.   The component (B) is selected from the group consisting of phosphate compounds, phosphonate compounds, phosphinate compounds, phosphine oxide compounds, phosphite compounds, phosphonite compounds, phosphinite compounds, phosphine compounds and condensed phosphate ester compounds. The fiber for flame-retardant polyester-based artificial hair according to claim 1 and 3, or claim 2 and 3, which is at least one compound. The component (B) is represented by the general formula (1):

(In the formula, R ¹ is a monovalent aromatic hydrocarbon group or aliphatic hydrocarbon group, and they may be the same or different. R ² is a divalent aromatic hydrocarbon group. And when two or more are included, they may be the same or different. N represents 0 to 15.)
The fiber for flame-retardant polyester-based artificial hair according to claim 1 or 3, which is a condensed phosphate compound represented by the formula: The reactive phosphorus flame retardant which is the component (B) copolymerizable with the component (A) is represented by the general formulas (2) to (7):

Wherein R ³ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, R ⁴ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, m Represents an integer of 1 to 11.)

(In the formula, R ⁵ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different.)

(In the formula, R ⁶ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ⁷ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. And they may be the same or different, and l represents an integer of 1 to 12.)

(In the formula, R ⁸ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ⁹ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. These may be the same or different, and p represents an integer of 1 to 11.)

(In the formula, R ¹⁰ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different. Y is a hydrogen atom, a methyl group or 6 carbon atoms. -12 aromatic hydrocarbon groups, r and s each represent an integer of 1 to 20)

(In the formula, R ¹¹ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ¹² is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. And they may be the same or different, and t represents an integer of 1 to 20.)
The fiber for flame-retardant polyester-based artificial hair according to claim 2 or 3, which is at least one selected from the group consisting of a phosphorus-containing compound represented by the formula:   The component (B) is a bromine-containing phosphate ester flame retardant, brominated polystyrene flame retardant, brominated benzyl acrylate flame retardant, brominated epoxy flame retardant, brominated polycarbonate flame retardant, tetrabromobisphenol A derivative, The flame retardant polyester artificial hair fiber according to claim 1 or 3, which is at least one compound selected from the group consisting of a bromine-containing triazine compound and a bromine-containing isocyanuric acid compound.   Component (C) is an ethylene-glycidyl (meth) acrylate copolymer, an ethylene-maleic anhydride copolymer, an ethylene-ethyl (meth) acrylate-maleic anhydride copolymer, an ethylene-methyl (meth) acrylate copolymer. Copolymer, ethylene-glycidyl (meth) acrylate copolymer-g-polystyrene, ethylene-glycidyl (meth) acrylate copolymer-g-polymethyl methacrylate, ethylene-glycidyl (meth) acrylate copolymer-g-acrylonitrile-styrene Copolymer, ethylene-ethyl (meth) acrylate-maleic anhydride copolymer-g-polystyrene, ethylene-ethyl (meth) acrylate-maleic anhydride copolymer-g-polymethyl methacrylate, ethylene-ethyl (meth) Acrylate-anhydrous malein Copolymer-g-acrylonitrile-styrene copolymer, montanic acid wax, montanic acid ester wax, partially saponified montanic acid wax, montanic acid metal salt, polyethylene wax, polyethylene oxide wax, polytetrafluoroethylene The fiber for flame-retardant polyester-based artificial hair according to any one of claims 1 to 7, which is an additive comprising at least one of fluorine-modified wax, polydimethylsilicone, and modified silicone resin.   The composition comprising the components (A), (B) and (C), or the composition comprising the components (C) and (D) is selected from the group consisting of an antimony trioxide compound, an antimony pentoxide compound and sodium antimonate. The fiber for flame-retardant polyester-based artificial hair according to any one of claims 1 to 8, wherein at least one of them is mixed as a flame-retardant aid (E).   Organic fine particles (F) and / or inorganic fine particles (G) were further mixed with the composition comprising the components (A), (B) and (C), or the composition comprising the components (C) and (D). The fiber for flame-retardant polyester-based artificial hair according to any one of claims 1 to 8, wherein the fiber surface has fine protrusions.   The flame retardant polyester-based artificial hair fiber according to claim 10, wherein the component (F) is at least one selected from the group consisting of polyarylate, polyamide, fluororesin, silicone resin, crosslinked acrylic resin, and crosslinked polystyrene.   The flame retardancy according to claim 10, wherein the component (G) is at least one selected from the group consisting of calcium carbonate, silicon oxide, titanium oxide, aluminum oxide, zinc oxide, talc, kaolin, montmorillonite, bentonite and mica. Polyester fiber for artificial hair.   The flame-retardant polyester-based artificial hair fiber according to any one of claims 1 to 12, wherein the flame-retardant polyester-based fiber has a non-crimped raw silk shape.   The fiber for flame-retardant polyester-based artificial hair according to any one of claims 1 to 13, wherein the flame-retardant polyester-based fiber is originally attached.   The flame-retardant polyester fiber according to any one of claims 1 to 14, which has a single fiber fineness of 30 to 80 dtex.