JP2007100237A - Flame-retardant polyester-based artificial hair - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester-based artificial hair produced with excellent spinning stability, maintaining the fiber properties such as strength and elongation of a usual polyester fiber, having excellent settability, touch feeling and combability, and also having excellent flame retardance. <P>SOLUTION: The flame-retardant polyester-based artificial hair is obtained by suppressing the formation of gel at the spinning by subjecting a composition containing a bromine-containing flame retardant, an antimony compound and a basic inorganic compound in a specific proportion in a polyester to melt spinning. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a flame-retardant polyester artificial hair formed from a composition comprising a polyester containing a bromine-containing flame retardant, an antimony compound and a basic inorganic compound. More specifically, the present invention relates to a flame-retardant polyester artificial hair excellent in setability, tactile sensation, and transparency, while suppressing gel generation during melt spinning and maintaining fiber properties such as high elongation.

  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. Modacryl has been frequently used as an artificial hair material taking advantage of flame retardancy, but it was insufficient in terms of heat-resistant temperature. In recent years, artificial hair using fibers mainly composed of polyester typified by polyethylene terephthalate having excellent heat resistance has been proposed. However, when using polyester as an artificial hair material, it is necessary to impart flame retardancy from the viewpoint of safety. Since conventional polyester fibers are flammable, various attempts have been made to improve the flame retardancy of polyester fibers. For example, polyester fibers copolymerized with a flame retardant monomer containing a phosphorus atom. And a method of incorporating a bromine-containing flame retardant into a polyester fiber are 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. Moreover, as what applied the said flame-retarding technique to artificial hair, the polyester fiber which copolymerized the phosphorus compound, for example is proposed (patent document 4). 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 bromine-containing flame retardant, a method of containing a fine halogenated cycloalkane compound in a polyester fiber (Patent Document 5), a method of containing a bromine atom-containing alkylcyclohexane (Patent Document 6). A method (Patent Document 7) containing a brominated epoxy flame retardant has been proposed. In the method of adding a bromine-containing 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 there is a problem that a large amount of a flame retardant has to be used, which causes problems such as a decrease in fiber properties, a decrease in productivity, and an increase in production cost for artificial hair.
Japanese Patent Publication No. 55-41610 Japanese Patent Publication No.53-13479 Japanese Patent Laid-Open No. 11-124732 JP-A-3-27105 Japanese Patent Publication No. 3-57990 Japanese Patent Publication No. 1-2913 JP 2005-42234 A

  For this reason, when using a bromine-containing flame retardant, it is a polyester for artificial hair that suppresses its content and ensures fiber properties such as high elongation, and satisfies the flame retardancy required for artificial hair. There is a need to.

  In order to improve the flame retardancy when such a bromine-containing flame retardant is used, it may be possible to add a flame retardant aid together with the bromine-containing flame retardant. It has been found that by using a compound in combination, excellent flame retardancy can be imparted even in the case of artificial hair with reduced flame retardant content.

  However, when melt spinning processing is performed using a composition containing a flame retardant material in which a flame retardant and a flame retardant aid are used in combination, the resulting fiber has defects that are considered to be derived from the gel at the time of melting. It was confirmed in some spun yarns from the beginning of spinning. The fiber properties of these fibers decrease at the gel part, so the desired fiber properties cannot be obtained despite the suppression of the content of bromine-containing flame retardant, and the gel-like protrusions give a feeling of softness to the touch. Therefore, there is a problem that the product becomes defective and the productivity is lowered. In addition, when melt spinning for a long time for mass production, it is clear that yarn breakage frequently occurs in the gel part in some spun yarns in which the formation of the gel was confirmed during discharge from the spinneret. became.

  An object of the present invention is to solve the above-mentioned problems, and it is difficult to combine a bromine-containing flame retardant with an antimony compound when producing polyester fiber for artificial hair by melt spinning. Improves flammability and suppresses the formation of gels during melt spinning, which reduces the physical properties of the fiber that occurs when the flame retardant material is used in combination. It is possible to provide polyester-based artificial hair that is capable of high melt spinning and maintains fiber properties such as high elongation of polyester fibers and is excellent in setability, touch and combing.

  As a result of intensive studies to solve the above problems, the present inventor has melt-spun a composition comprising a bromine-containing flame retardant, an antimony compound and a basic inorganic compound in a predetermined composition in the polyester, The production of gels that reduce the physical properties of fibers that occur during melt spinning is suppressed, high-productivity melt spinning is possible with no yarn breakage even when long-term production is performed, and high-stretching of ordinary polyester fibers The present inventors have found that a flame-retardant polyester artificial hair that maintains fiber physical properties such as degree and is excellent in setability, tactile sensation, and transparency can be obtained.

  That is, the present invention relates to a bromine-containing flame retardant (B) 5 to 30 parts by mass, antimony with respect to 100 parts by mass of polyalkylene terephthalate or polyester (A) composed of one or more copolyesters mainly composed of polyalkylene terephthalate. The present invention relates to a polyester-based artificial hair formed from a composition comprising 0.5 to 10 parts by mass of a compound (C) and 0.01 to 3 parts by mass of a basic inorganic compound (D). Preferably, the polyester (A) is at least one polymer selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate, and the bromine-containing flame retardant (B) is a brominated aromatic. Flame retardant, brominated phosphate ester flame retardant, brominated polystyrene flame retardant, brominated benzyl acrylate flame retardant, brominated epoxy flame retardant, brominated phenoxy flame retardant, brominated polycarbonate flame retardant, tetra The polyester artificial hair and antimony compound (C), which are at least one compound selected from the group consisting of a bromobisphenol A derivative, a bromine-containing triazine compound, and a bromine-containing isocyanuric acid compound, are antimony trioxide, tetraoxide Antimony, pentaacid The polyester-based artificial hair and the basic inorganic compound (D), which are at least one antimony compound selected from the group consisting of antimony and sodium antimonate, are alkali metals, alkaline earth metals, periodic table 3 The above-mentioned polyester-based artificial hair, which is a compound comprising at least one selected from the group consisting of group metal oxides, hydroxides, carbonates, and hydrotalcites, and the basic inorganic compound (D) is magnesium oxide Further, the present invention relates to the above polyester-based artificial hair that is at least one selected from the group consisting of magnesium hydroxide and hydrotalcite.

  Furthermore, this invention relates to the said polyester type artificial hair containing 0.1-5 mass parts of organic fine particles (E) and / or inorganic fine particles (F) with respect to 100 mass parts of polyester (A).

  According to the present invention, since a bromine-containing flame retardant and an antimony compound are used as a flame retardant material and a basic inorganic compound is contained, when the polyester fiber for artificial hair is produced by melt spinning, Fibers that reduce the physical properties of fibers generated by the combined use of fuel materials are suppressed during the melt spinning process, and can be produced for a long time without yarn breakage. Polyester artificial hair that maintains physical properties, is excellent in setability, touch, and combing properties and has high flame retardancy can be obtained.

  Moreover, this invention can reduce manufacturing cost by using at least 1 sort (s) of polymer chosen from the group which consists of a polyethylene terephthalate, a polypropylene terephthalate, and a polybutylene terephthalate as a polyalkylene terephthalate.

  Further, the present invention provides a brominated aromatic flame retardant (B), brominated aromatic flame retardant, brominated phosphate ester flame retardant, brominated polystyrene flame retardant, brominated benzyl acrylate flame retardant, brominated epoxy. At least one flame retardant selected from the group consisting of a flame retardant, a brominated phenoxy flame retardant, a brominated polycarbonate flame retardant, a tetrabromobisphenol A derivative, a bromine-containing triazine compound, and a bromine-containing isocyanuric acid compound In addition, flame retardants that easily generate gels when used in combination with antimony compounds, particularly brominated epoxy flame retardants, brominated phenoxy flame retardants, brominated polycarbonate flame retardants, and the like can also be used.

  Furthermore, the present invention provides a bromine-containing compound by using at least one antimony compound selected from the group consisting of antimony trioxide, antimony tetroxide, antimony pentoxide and sodium antimonate as the antimony compound (C). Even if there is little content of a flame retardant, sufficient flame retardance can be provided.

  And this invention is a group which consists of an alkali metal, alkaline earth metals, the oxide of a periodic table group 3 metal, a hydroxide, carbonate, and a hydrotalcite as a basic inorganic compound (D). By using at least one compound selected from the group consisting of at least one selected from the group consisting of magnesium oxide, magnesium hydroxide and hydrotalcite, gel generation can be further reduced.

  In addition, this invention contains 0.1-5 mass parts of organic fine particles (E) and / or inorganic fine particles (F) with respect to 100 mass parts of the said polyester (A), and is fine on the surface of the fiber obtained. Protrusions can be formed to adjust the gloss and gloss of the fiber surface.

  The flame-retardant polyester-based artificial hair of the present invention comprises a polyalkylene terephthalate or a polyester (A) composed of one or more copolymer polyesters mainly composed of polyalkylene terephthalate, a bromine-containing flame retardant (B), an antimony compound (C ) And a basic inorganic compound (D). A fiber formed by melt spinning.

  Examples of the polyalkylene terephthalate contained in the polyester (A) used in the present invention or a copolymerized polyester mainly composed of polyalkylene terephthalate include polyalkylene terephthalates such as polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate and / or these. Examples thereof include copolymer polyesters mainly composed of polyalkylene terephthalate and containing a small amount of a copolymer component. As the polyalkylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate are preferable from the viewpoint of availability and cost. In addition, the said main body means containing 80 mol% or more.

  Examples of the copolymer component include isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid, trimellitic acid, pyromellitic acid, succinic acid, glutaric acid, adipic acid, superic acid, azelaic acid, sebacin Acids, 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 copolymerized polyester is usually produced by reacting a main component of terephthalic acid and / or a derivative thereof (for example, methyl terephthalate) with a polymer of alkylene glycol containing a small amount of a copolymer component. However, it is preferable from the viewpoint of stability and ease of operation, but 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 copolymerized 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, copolymer 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 the polyester (A) used in the present invention is preferably 0.5 to 1.4, and more preferably 0.6 to 1.2. When the intrinsic viscosity of the polyester (A) is less than 0.5, the mechanical strength of the resulting fiber tends to decrease. When it exceeds 1.4, the melt viscosity increases with increasing molecular weight, It tends to be difficult and the fineness becomes uneven.

  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 bromine-containing flame retardant (B) in the present invention include bromine-containing phosphate ester flame retardant, brominated polystyrene flame retardant, brominated benzyl acrylate flame retardant, brominated epoxy flame retardant, brominated phenoxy Flame retardants, brominated polycarbonate flame retardants, tetrabromobisphenol A derivatives, bromine-containing triazine compounds, bromine-containing isocyanuric acid compounds are preferred, and bromine-containing phosphates from the standpoint of fiber properties, heat resistance and processing stability A flame retardant, a brominated epoxy flame retardant, and a brominated phenoxy resin flame retardant are more preferable. When using brominated epoxy flame retardant, brominated phenoxy flame retardant, brominated polycarbonate flame retardant which is easy to gel when used in combination with antimony compound while having excellent flame retardancy among the above bromine-containing flame retardants In particular, the present invention is particularly useful, and brominated epoxy flame retardants are also preferable because of their excellent compatibility with polyesters.

  Specific examples of the bromine-containing flame retardant (B) include, for example, pentabromotoluene, hexabromobenzene, decabromodiphenyl, decabromodiphenyl ether, bis (tribromophenoxy) ethane, tetrabromophthalic anhydride, ethylenebis Bromine-containing phosphates such as (tetrabromophthalimide), ethylenebis (pentabromophenyl), octabromotrimethylphenylindane, tris (tribromoneopentyl) phosphate, brominated polystyrenes represented by the general formula (1) Brominated polybenzyl acrylates represented by general formula (2), brominated epoxy oligomers represented by general formula (3), brominated phenoxy resins, brominated polycarbonate oligomers represented by general formula (4) , Tetrabromobisphe Tetrabromobisphenol A derivatives such as A, tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (allyl ether), tetrabromobisphenol A-bis (hydroxyethyl ether), Examples thereof include bromine-containing triazine compounds such as tris (tribromophenoxy) triazine and bromine-containing isocyanuric acid compounds such as tris (2,3-dibromopropyl) isocyanurate. These may be used alone or in combination of two or more.

（式中、Ｙは１〜５、ｎは５〜２００を示す）

(In the formula, Y represents 1 to 5, and n represents 5 to 200)

（式中、ｍは５〜１００を示す）

(In the formula, m represents 5 to 100)

（式中、Ｒ^１は炭素数１〜１０の炭化水素基、アリール基、アラルキル基、反応性基を含む炭化水素基、臭素含有アリール基、または臭素含有アラルキル基であり、それらはそれぞれ同一であってもよく異なっていてもよい、ｐは１〜８０を示す）

(In the formula, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, a hydrocarbon group containing a reactive group, a bromine-containing aryl group, or a bromine-containing aralkyl group, which are the same. Or may be different, p represents 1 to 80)

（式中、Ｒ^２は水素または臭素原子であり、それらはそれぞれ同一であってもよく異なっていてもよい、ｑは１〜８０を示す）

(Wherein R ² is a hydrogen atom or a bromine atom, and they may be the same or different from each other, q represents 1 to 80)

  5-30 mass parts is preferable with respect to 100 mass parts of polyester (A), and, as for the usage-amount of the bromine containing flame retardant (B) in this invention, 6-25 mass parts is more preferable, and 7-20 mass parts is further more preferable. . When the amount of the bromine-containing flame retardant (B) used is less than 5 parts by mass, the flame retardant effect tends to be difficult to obtain. When the amount exceeds 30 parts by mass, the mechanical properties, heat resistance, and drip resistance of the resulting fiber are reduced. There is a tendency to be damaged.

  In this invention, although a flame retardance is expressed by mix | blending a bromine containing flame retardant (B) component, a flame retardant effect improves remarkably by mix | blending an antimony type compound (C) component.

  The antimony compound (C) used in the present invention is not particularly limited, and specific examples include antimony trioxide, antimony tetroxide, antimony pentoxide, and sodium antimonate. Among these, sodium antimonate is preferable from the viewpoint of the spinnability of the composition.

  The average particle size of the antimony compound (C) in the present invention is preferably 0.02 to 15 μm, more preferably 0.1 to 12 μm, and further preferably 0.2 to 10 μm.

  The antimony compound (C) in the present invention may be surface-treated with an epoxy compound, a silane compound, an isocyanate compound, a titanate compound, or the like, if necessary.

  0.5-10 mass parts is preferable with respect to 100 mass parts of polyester (A), and, as for the usage-amount of the antimony type compound (C) in this invention, 0.6-9 mass parts is more preferable, and 0.7-7 Part by mass is more preferable. When the amount of the antimony compound (C) used is less than 0.5 parts by mass, the improvement in flame retardancy tends to be small, and when it exceeds 10 parts by mass, the processing stability is improved even when a basic inorganic compound is used. Inferior, appearance and transparency tend to be impaired.

  In the present invention, by using the basic inorganic compound (D) together with the bromine-containing flame retardant (B) and the antimony compound (C), gel generation at the time of melt spinning can be suppressed, and the fiber Since the physical properties are not deteriorated and troubles during spinning such as yarn breakage can be reduced even in production for a long time, the spinning stability is improved and a filament having good yarn properties can be obtained.

  That is, by using the bromine-containing flame retardant (B) and the antimony compound (C) in combination, the flame resistance of the resulting polyester fiber is remarkably improved. However, the composition containing these flame retardant materials is melt-spun. In this case, defects in the melted gel have occurred in some of the spun yarn discharged from the nozzle holes located near both ends of the spinneret from the beginning of spinning. Thread breakage was confirmed. The above phenomenon was hardly observed in the composition containing only the bromine-containing flame retardant without containing the antimony compound, so that the melt was modified by the combined use of the bromine-containing flame retardant and the antimony compound. It was thought that there was.

  The reason for the modification of the melt is not clear, but in the presence of an antimony compound, the reaction derived from the terminal carboxylic acid of the polyester is accelerated. For example, when a brominated epoxy flame retardant is used, The present inventor speculates that the molecular weight of the polyester may be partially increased by the reaction between the carboxylic acid terminal and the epoxy group due to the occasional superheating at a high temperature.

  For this reason, as a result of various investigations on the suppression of gel formation that occurs when the bromine-containing flame retardant and the antimony compound are used in combination, the present invention further modifies the melt by adding a basic inorganic compound. Thus, the flame retardancy can be improved without lowering the fiber physical properties, and the occurrence of defective products is reduced to ensure high productivity.

  The basic inorganic compound (D) used for this invention does not have limitation in particular, If it is generally used, it can be used.

  Specific examples of the basic inorganic compound (D) in the present invention include alkali metals, alkaline earth metals, Group 3 metal oxides, hydroxides, carbonates, and hydrotalcites of the periodic table. And at least one compound selected from the group, for example, metal oxides such as lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, barium oxide, aluminum oxide, lithium hydroxide, sodium hydroxide, water Metal hydroxides such as potassium oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, aluminum hydroxide, metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, aluminum carbonate And hydrotalcite. These compounds may be used alone or in combination of two or more.

  Among the above, at least one selected from the group consisting of magnesium oxide, magnesium hydroxide and hydrotalcite is preferable, and magnesium oxide or magnesium hydroxide is more preferable from the viewpoint of the effect of suppressing gel formation during melt spinning.

  The amount of the basic inorganic compound (D) used in the present invention is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2.5 parts by mass, with respect to 100 parts by mass of the polyester (A). 1 to 2 parts by mass is more preferable. When the amount of the basic inorganic compound (D) used is less than 0.01 parts by mass, a gel is generated during melt spinning, thread breakage occurs, or gel-derived protrusions remain on the fiber surface, resulting in decreased tactile sensation. When a tendency is generated and the amount exceeds 3 parts by mass, the spinning stability is lowered due to a decrease in melt viscosity and yarn breakage occurs, and mechanical properties, heat resistance, flame retardancy, and drip resistance tend to be impaired.

  The flame-retardant polyester-based artificial hair of the present invention further forms fine protrusions on the surface of the fiber obtained by mixing organic fine particles (E) and / or inorganic fine particles (F) in addition to the above composition, The gloss and gloss of the fiber surface can be adjusted.

  The organic fine particles (E) in the present invention can be used as long as they are organic resins having a structure that is incompatible with or partially incompatible with the flame retardant polyester (A) as the main component. Polyarylate, polyamide, fluororesin, silicone resin, crosslinked acrylic resin, crosslinked polystyrene and the like are preferably used. These may be used alone or in combination of two or more. In order to stably exhibit the gloss adjusting effect, crosslinked polyester particles and crosslinked acrylic particles are preferable from the viewpoint of heat resistance and dispersibility.

The crosslinked polyester particles can be obtained by dispersing an unsaturated polyester and a vinyl monomer in water and crosslinking and curing. The unsaturated polyester used here is not particularly limited, and examples thereof include those obtained by polymerizing an α, β-unsaturated acid or a mixture thereof with a dihydric alcohol or a trihydric alcohol. Can do. Examples of the unsaturated acids, e.g., fumaric acid, maleic acid, include itaconic acid, the saturated acids, such as phthalic acid, terephthalic acid, succinic acid, glutaric acid, tetrahydrophthalic acid, adipic acid, sebacic Thin An acid etc. are mentioned. Examples of the dihydric alcohol and trihydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, 1,3-propanediol, 1,6-hexanediol, and trimethylolpropane. On the other hand, the vinyl monomer is not particularly limited, and examples thereof include styrene, chlorostyrene, vinyl toluene, divinylbenzene, acrylic acid, methyl acrylate, acrylonitrile, ethyl acrylate, and diallyl phthalate.

  The crosslinked acrylic particles can be obtained by water-dispersing an acrylic monomer and a crosslinking agent and crosslinking and curing. Examples of acrylic monomers used herein include acrylic acid or derivatives of acrylic acid, such as methyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, hydroxyethyl acrylate, acrylonitrile, acrylamide, N- Methylolacrylamide, or methacrylic acid or a derivative of methacrylic acid, such as methyl methacrylate, butyl methacrylate, hexyl methacrylate, glycidyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, N-vinyl-2-pyrrolidone methacrylate, methacrylo Examples thereof include vinyl monomers having one vinyl group in one molecule such as nitrile, methacrylamide, N-methylol methacrylamide, and 2-hydroxyethyl methacrylate. These can be used alone or in combination of two or more. Further, the crosslinking agent may be any monomer as long as it has two or more vinyl groups in one molecule, but one having two vinyl groups in one molecule is preferable. Preferred monomers include, for example, divinylbenzene, reaction products of glycol and methacrylic acid or acrylic acid (for example, ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, etc.), but are not limited thereto. It is not a thing. The addition amount of the crosslinking agent is preferably 0.02 to 5 parts by mass with respect to 100 parts by mass of the monomer having one vinyl group. The polymerization initiator is preferably a peroxide radical polymerization initiator, and examples thereof include benzoyl peroxide, 2-ethylhexyl perbenzoate, di-tert-butyl peroxide, cumene hydroperoxide, and methyl ethyl ketone peroxide. The radical polymerization initiator is preferably used in an amount of 0.05 to 10 parts by mass with respect to 100 parts by mass of the monomer having one vinyl group.

  As the inorganic fine particles (F) used in the present invention, those having a refractive index close to the refractive index of the flame retardant polyester (A) are preferable from the viewpoint of the effect on the transparency and color developability of the fiber. Examples thereof include silicon oxide, titanium oxide, aluminum oxide, zinc oxide, talc, kaolin, montmorillonite, bentonite and mica. These may be used alone or in combination of two or more. Among these, fine particles close to a sphere have a higher gloss adjusting effect, and silicon oxide, composite particles mainly composed of silicon oxide, and the like are preferable. The inorganic fine particles (F) used in the present invention may be surface-treated with an epoxy compound, a silane compound, an isocyanate compound, a titanate compound or the like as necessary.

  The amount of the organic fine particles (E) and / or inorganic fine particles (F) used in the present invention is not particularly limited, but is 0.1 to 5 parts by mass as a combined amount with respect to 100 parts by mass of the polyester (A). Preferably, 0.2-3 mass parts is more preferable, and 0.3-2 mass parts is further more preferable. When the amount of organic fine particles (E) and / or inorganic fine particles (F) used exceeds 5 parts by mass, appearance, hue and color developability tend to be impaired. Since there are fewer fine protrusions, the gloss adjustment of the fiber surface tends to be insufficient.

  The polyester-based artificial hair obtained by the present invention can be obtained by, for example, dry blending the components (A), (B), (C) and (D), and further the components (E) or (F). A polyester composition obtained by melt kneading using a simple kneader can be obtained by melt spinning using a single screw extruder.

  Examples of the kneader used for the production of the resin composition include, for example, 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.

  For example, using a twin screw extruder with a screw diameter of 45 mm, the barrel temperature is 260 to 300 ° C., the discharge amount is 50 to 150 kg / hr, the melt is kneaded at a screw rotation speed of 150 to 200 rpm, the strand is taken out from the die, and water-cooled. Later, the composition of the present invention can be obtained by pelletizing with a strand cutter.

  When the polyester-based artificial hair of the present invention is melt-spun by a normal melt-spinning method, for example, the temperature of an extruder, a gear pump, a base, etc. is set to 270 to 310 ° C., melt-spun, and the spun yarn is heated to a heating cylinder. And then cooled to below the glass transition point and taken up at a speed of 50 to 5000 m / min to obtain a spun yarn. 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.

  In addition, a composition obtained by dry blending the components (A), (B), (C) and (D), and further the component (E) or (F) is twin-screw extruder or kneaded equipped with a gear pump and a spinning nozzle. It can be obtained by melt spinning using a single screw extruder using a screw having a function without taking out the resin composition once.

  Further, after the components (A), (C) and (D), and also the components (E) and (F) are melt-kneaded, melt-spun and fiberized, the component (B) is subjected to exhaust processing. The polyester-based artificial hair of the invention can be obtained.

  In the present invention, the obtained spun yarn is hot-drawn, but the drawing is a two-step method in which the spun yarn is once wound and then drawn, and the direct spinning drawing in which the drawn yarn is continuously drawn without being wound. It may be by the method of law. 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.

  The polyester-based artificial hair of the present invention may contain various additives such as a light stabilizer, a fluorescent agent, an antistatic agent, a pigment, a plasticizer, and a lubricant as necessary.

  The fineness of the polyester artificial hair of the present invention thus obtained is usually 10 to 100 dtex, more preferably 20 to 90 dtex, which is suitable for artificial hair. Moreover, as artificial hair, it has the heat resistance which can use a beauty heat instrument (hair iron) at 160-200 degreeC, it is hard to ignite, and it is preferable to have self-extinguishing property.

  The polyester-based artificial hair of the present invention can be used by coloring it by dyeing or priming. When coloring by dyeing, it can be dyed under the same conditions as ordinary polyester fibers. In addition, in the case of the original attachment, the original attachment fiber can be obtained by melt-kneading the pigment used for a normal polyester fiber.

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

  The 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 flame-retardant polyester 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.

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

In addition, the measuring method of a characteristic value is as follows.
(Spinning workability)
Under the conditions described later, undrawn spun yarn obtained from a melt spinning machine is continuously taken out and visually evaluated for the presence or absence of yarn breakage.
○: There is no thread breakage for more than 1 hour. △: 1 thread breakage occurs within 2 hours. ×: 3 thread breakage occurs during 1 hour

(Strength and elongation)
The tensile strength / elongation of the filament is measured using a tensile / compression tester (manufactured by Intesco, INTESCO Model 201 type). A filament having a length of 40 mm is taken, and 10 mm on both ends of the filament is sandwiched with a backing sheet (thin paper) to which a double-sided tape glued with an adhesive is applied, 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, and the tensile strength and elongation at break are measured. The test is repeated 10 times under the same conditions, and the average value is defined as the filament elongation.

(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 feeling of roughness of the filament surface.
○: No rough feeling △: Some rough feeling ×: There is rough 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.
A: No resistance at all (very light)
○: Almost no resistance (light)
Δ: Some resistance (heavy)
×: There is considerable resistance or it gets caught in the middle

(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 with an effective length of 120 mm, burned, and evaluated as follows.
-Flammability-
A: After flame time is 0 seconds (no ignition)
○: After flame time is less than 3 seconds Δ: After flame time is 3 to 10 seconds ×: After flame time is 10 seconds or more

(Limited oxygen index LOI)
A 16 cm / 0.25 g filament is weighed, and the ends are lightly gathered with double-sided tape, and sandwiched and twisted with a suspender. When the twist is sufficient, fold the middle of the sample in two and twist the two. The end is fixed with cello tape (registered trademark) so that the total length becomes 7 cm. Pre-drying is performed at 105 ° C. for 60 minutes, and further drying is performed for 30 minutes or more in a desiccator. The dried sample is adjusted to a predetermined oxygen concentration, and after 40 seconds, ignited from the top with an igniter throttled to 8 to 12 mm, and the igniter is released after ignition. The oxygen concentration that burns for 5 cm or more or continues burning for 3 minutes or more is examined, and the test is repeated three times under the same conditions to obtain the limiting oxygen index (LOI).

(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.
Fusing between filaments ○: No fusing △: Slight fusing ×: Fusing with shrinkage / thread breakage ○: No shrinkage, no thread breakage △: Slightly shrinking, thread breakage ×: Folding, thread Broken rod out ○: The iron rod comes out smoothly △: The iron rod is slightly difficult to remove ×: The iron rod is difficult to remove ○: The curl shape is maintained Δ: The curl shape is slightly broken ×: The curl shape collapses

The raw materials used in the examples and comparative examples are as follows.
Polyester (A):
-Polyethylene terephthalate, manufactured by Mitsubishi Chemical Corporation, BK-2180
Bromine-containing flame retardant (B):
-Brominated epoxy flame retardant, Sakamoto Pharmaceutical Co., Ltd., SR-T20000
Antimony compound (C):
-Antimony trioxide, manufactured by Nippon Seiko Co., Ltd., PATOX-P, average particle size (primary particle) 3 μm
・ Sodium antimonate, manufactured by Nippon Seiko Co., Ltd., SA-A, average particle size (primary particle) 2.4 μm
Basic inorganic compound (D):
・ Magnesium oxide, manufactured by Kyowa Chemical Co., Ltd., Pyroxuma 5Q
・ Magnesium hydroxide, manufactured by Kyowa Chemical Co., Ltd., Kisuma 5Q
-Hydrotalcite, manufactured by Kyowa Chemical Co., Ltd., DHT-4C
Inorganic fine particles (F):
・ Fine silica, manufactured by Fuji Silysia Chemical Co., Ltd., Silicia 310P
Pigment:
-Pigment master batch, carbon black 20wt%, manufactured by Dainichi Seika Kogyo Co., Ltd., PESM22367BLACK
Hydrophilic fiber treatment agent:
・ Random copolymer polyether of ethylene oxide-propylene oxide, manufactured by Maruhishi Oil Chemical Co., Ltd., KWC-Q
・ Cationic surfactant, manufactured by Maruhishi Oil Chemical Co., Ltd., processing agent 29

(Examples 1 to 15)
The composition shown in Table 1 (each numerical value means part by mass) was dried to a water content of 100 ppm or less, dry blended, and then into a twin screw extruder (manufactured by Nippon Steel Works, Ltd., TEX44). The mixture was melted and kneaded at a cylinder set temperature of 280 ° C., pelletized, and dried to a water content of 100 ppm or less.

  Next, using a melt spinning machine (SV30, manufactured by Shinko Machinery Co., Ltd.), the molten polymer is discharged from a spinneret having a rectangular cross-section nozzle hole with a flatness ratio of 1.4: 1 at a cylinder setting temperature of 280 ° C. Then, it was air-cooled with cooling air at 20 ° C. and wound at a speed of 100 m / min to obtain an undrawn yarn. The obtained unstretched yarn is stretched 4 times using a heat roll heated to 85 ° C., heat treated using a heat roll heated to 200 ° C., wound at a speed of 30 m / min, and single fiber A polyester fiber (multifilament) having a fineness of about 50 dtex was obtained.

  Further, the obtained polyester fiber was used as a tow filament having a total fineness of 100,000 dtex, and after attaching the following aqueous solution so as to have a liquid content of 25% with respect to the weight of the tow, a hot air dryer was used. Dry at 10 ° C. for 10 minutes. In addition, as the aqueous solution, each of the pure fibers so that the exhaust amount of the hydrophilic fiber treatment agent KWC-Q and the processing agent 29 is 0.20% omf on the finally obtained polyester fiber, respectively. An aqueous solution containing 0.8% was prepared. The aqueous solution was adhered to the obtained tow filament with a total fineness of 100,000 dtex so that the liquid content was 25% based on the weight of the tow, and dried at 120 ° C. for 10 minutes with a hot air dryer.

  Table 2 shows the results of evaluating the fiber elongation and tactile sensation, combing resistance, flame retardancy and iron setability using the fiber spinning processability.

(Comparative Examples 1-4)
Polyester fibers (multifilaments) having a single fiber fineness of around 50 dtex were obtained from the compositions having the blending ratios shown in Table 1 in the same manner as in the Examples.

  Table 2 shows the results of evaluating spinning processability, high elongation, tactile sensation, combing, flame retardancy, and iron setability in the same manner as in the examples. In Comparative Examples 2 and 3, since the spinning processability was inferior, the evaluation of flame retardancy and iron setability was not performed because of high elongation, tactile sensation, and comb.

  As shown in Table 2, in contrast to the comparative example, in the examples, by using a basic inorganic compound together with a bromine-containing flame retardant and an antimony compound, gel generation during melt spinning can be suppressed. It was also confirmed that spinning trouble such as yarn breakage can be reduced, so that spinning stability can be improved and productivity can be improved. Furthermore, it was confirmed that polyester fibers for artificial hair exhibiting high flame retardance without deterioration of iron setability and the like, having good tactile sensation and combing without formation of gel-derived protrusions on the fiber surface were confirmed. . Therefore, the artificial hair obtained from the composition of the present invention has excellent spinning stability, and has improved tactile sensation, combing property, setability and flame retardancy while maintaining the mechanical properties and thermal properties of polyester. It can be effectively used as hair.

Claims (8)

  The bromine-containing flame retardant (B) 5 to 30 parts by mass, the antimony compound (C) 0 with respect to 100 parts by mass of the polyalkylene terephthalate or polyester (A) comprising at least one of the copolyesters based on polyalkylene terephthalate. Flame-retardant polyester artificial hair formed from a composition containing 5 to 10 parts by mass and 0.01 to 3 parts by mass of a basic inorganic compound (D).   The flame-retardant polyester artificial hair according to claim 1, wherein the polyalkylene terephthalate is at least one polymer selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate.   The bromine-containing flame retardant (B) is brominated aromatic flame retardant, bromine-containing phosphate ester flame retardant, brominated polystyrene flame retardant, brominated benzyl acrylate flame retardant, brominated epoxy flame retardant, bromine The flame retardant is a fluorinated flame retardant, a brominated polycarbonate flame retardant, a tetrabromobisphenol A derivative, a bromine-containing triazine compound, or a bromine-containing isocyanuric acid compound. The flame-retardant polyester artificial hair described in 1.   The bromine-containing flame retardant (B) is at least one flame retardant selected from the group consisting of brominated epoxy flame retardants, brominated phenoxy flame retardants and brominated polycarbonate flame retardants. The flame-retardant polyester artificial hair described.   5. The antimony compound (C) is at least one antimony compound selected from the group consisting of antimony trioxide, antimony tetroxide, antimony pentoxide, and sodium antimonate. The flame-retardant polyester artificial hair described.   The basic inorganic compound (D) is at least one selected from the group consisting of alkali metals, alkaline earth metals, Group 3 metal oxides, hydroxides, carbonates, and hydrotalcites of the periodic table. The flame-retardant polyester artificial hair according to any one of claims 1 to 5, which is a seed compound.   The flame retardant polyester according to any one of claims 1 to 5, wherein the basic inorganic compound (D) is at least one compound selected from the group consisting of magnesium oxide, magnesium hydroxide and hydrotalcite. Artificial hair.   Furthermore, the difficulty of any one of Claims 1-7 which contains 0.1-5 mass parts of organic fine particles (E) and / or inorganic fine particles (F) with respect to 100 mass parts of said polyester (A). Flammable polyester-based artificial hair.