JP2006144184A - Flame-retardant polyester-based artificial hair - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester-based fiber for artificial hair, excellent in flame retardancy, setting properties, and dripping resistance, while maintaining heat resistance and fiber characteristics, including tensile strength and elongation, of ordinary polyester fibers, and controlled in luster of the fiber, and to provide the artificial hair given by using the same. <P>SOLUTION: This polyester-based fiber is formed by melt-spinning a composition which is obtained by melting and kneading 100 pts.wt. of a polyester (A) with 5-50 pts.wt. of a polymeric flame retardant (B), wherein the polyester (A) comprises a polyalkylene terephthalate and one or more kinds of copolymerized polyesters consisting mainly of the polyalkylene terephthalate and the polymeric flame retardant (B)contains a phosphorus element-containing monomer component (b1) and/or a bromine element-containing monomer component (b2) as main structural units and is formed by copolymerizing the components with each other through ester bonds. Thus, the polyester-based artificial hair which is excellent in the flame retardancy, the setting properties, and the dripping resistance, while maintains the heat resistance and the fiber characteristics, including the tensile strength and elongation, of the ordinary polyester fibers, and is controlled in the luster of the fiber is obtained. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention provides a monomer component (b1) in which the main structural unit contains a phosphorus element and / or a monomer that contains a bromine element in a polyester comprising at least one of polyalkylene terephthalate and a copolymerized polyester mainly composed of polyalkylene terephthalate. The present invention relates to a flame-retardant polyester artificial hair formed from a composition obtained by melt-kneading a polymer flame retardant which is a component (b2) and copolymerized by an ester bond. More specifically, the present invention relates to 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.

  Conventionally, human hair, artificial hair (modacrylic fiber, polyvinyl chloride fiber) and the like have been used in hair products such as wigs, hair wigs, false hairs, hair bands and 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 to improve the flame resistance of polyester fibers have been made, for example, a method of impregnating a polyester fiber with a flame retardant by post-processing, a method of kneading a flame retardant during melt-kneading or spinning, A method of copolymerizing a flame retardant monomer containing a phosphorus atom at the time of polymerization is known.

  As a method for incorporating a flame retardant into a polyester fiber by post-processing, a method of incorporating a fine halogenated cycloalkane compound into a polyester fiber (Patent Document 1), a method of incorporating a bromine atom-containing alkylcyclohexane (Patent Document 2). In order to obtain sufficient flame resistance, it is necessary to increase the content treatment temperature to 150 ° C. or higher, or the content treatment time needs to be long, or a large amount There are problems such as having to use other flame retardants, and problems that the flame retardants are eluted by washing and shampooing, causing problems such as decreased fiber properties, decreased productivity, and increased manufacturing costs. Will occur.

  Moreover, as a method of kneading a flame retardant at the time of melt-kneading or spinning, there is a method of obtaining a flame-retardant polyester fiber by spinning a composition obtained by melt-kneading a phosphoric ester-based flame retardant to polyester (Patent Document 3). Although it has been proposed, there is a problem that the fiber surface has a sticky feeling or the flame retardant is eluted by washing or shampooing.

  Furthermore, as a method of copolymerizing a flame retardant monomer, polyester fibers copolymerized with a phosphorus compound (Patent Documents 4 and 5) and the like have been proposed, but in order to obtain sufficient flame retardancy, The amount of copolymerization must be increased. As a result, the heat resistance of the polyester is greatly reduced, and when melt spinning becomes difficult or the flame approaches, it does not ignite or burn, but melts and drip. A problem occurs.

Various proposals have been made in the past, but in order to ensure the high flame resistance required for artificial hair, it is necessary to use a large amount of flame retardant in any of the methods. It was difficult to maintain fiber properties such as properties and strong elongation. From these facts, it is actually the case that artificial hair that maintains the physical properties of fibers such as heat resistance and tensile strength of conventional polyester fibers and is excellent in flame retardancy, setability and combing properties has not been obtained yet. .
Japanese Patent Publication No. 3-57990 Japanese Patent Publication No. 1-2913 JP-A-9-268423 JP-A-3-27105 JP-A-5-339805

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

  As a result of intensive studies in order to solve the above problems, the present inventors have found that the main structural unit contains a phosphorus element in a polyester composed of at least one of polyalkylene terephthalate and a copolymerized polyester mainly composed of polyalkylene terephthalate. A monomer component containing and / or a monomer component containing elemental bromine, and melt spinning a composition obtained by melt-kneading a polymer flame retardant copolymerized by an ester bond. We have found that it is possible to obtain flame-retardant polyester-based artificial hair fibers that maintain fiber properties such as heat resistance and high elongation, are excellent in flame retardancy, setability and drip resistance, and have a controlled fiber gloss. The present invention has been completed.

  That is, the present invention provides a monomer component (b1) in which the main structural unit contains a phosphorus element with respect to 100 parts by weight of a polyester (A) composed of at least one of polyalkylene terephthalate and a copolymerized polyester mainly composed of polyalkylene terephthalate. And / or a monomer component (b2) containing elemental bromine, which is formed from a composition obtained by melt-kneading 5 to 50 parts by weight of a polymer flame retardant (B) copolymerized by an ester bond Flammable polyester-based artificial hair, preferably, component (A) is at least one polymer selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate, and component (B) has the following general formula: (1) to (3)

（式中、Ｒ¹は炭素数２〜１０の直鎖または分岐を含む脂肪族炭化水素基または炭素数６〜１２の芳香族炭化水素基、Ｒ²は炭素数６〜１２の芳香族炭化水素基、Ａはリン元素または臭素元素を含む原子団、ｍ／ｎ＝６０／４０〜９５／５である。）

(In the formula, R ¹ is an aliphatic hydrocarbon group including a straight chain or branched chain having 2 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ² is an aromatic hydrocarbon group having 6 to 12 carbon atoms. Group A is an atomic group containing phosphorus element or bromine element, m / n = 60/40 to 95/5.)

The number average molecular weight of the component (B) is 5000 to 80000, the content of the component (b1) and / or (b2) in the component (B) is 60 to 95 mol%, the component (b1), ( The component b2) has a structure represented by the following general formulas (4) to (6),

（式中、Ｒ³は水素原子または炭素数１〜２０の脂肪族炭化水素基、Ｒ⁴は水素原子または炭素数１〜２０の脂肪族炭化水素基であり、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、Ａはリン元素または臭素元素を含む原子団を示す。）

Wherein R ³ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, R ⁴ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, (A may be different, and A represents an atomic group containing phosphorus element or bromine element.)

（式中、Ｒ⁵は炭素数１〜２０の脂肪族炭化水素基または炭素数６〜１２の芳香族炭化水素基、Ｒ⁶、Ｒ⁷は水素原子又は炭素数１〜２０の脂肪族炭化水素基、ｐは１〜１１の整数を示す。）

（式中、Ｒ⁸は水素原子又は炭素数１〜２０の脂肪族炭化水素基であり、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）

（式中、Ｒ⁹は炭素数１〜２０の脂肪族炭化水素基または炭素数６〜１２の芳香族炭化水素基、Ｒ¹⁰は水素原子又は炭素数１〜２０の脂肪族炭化水素基であり、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、ｒは１〜１２の整数を示す）

（式中、Ｒ¹¹は炭素数１〜２０の脂肪族炭化水素基または炭素数６〜１２の芳香族炭化水素基、Ｒ¹²は水素原子又は炭素数１〜２０の脂肪族炭化水素基であり、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、ｓは１〜１１の整数を示す）

（式中、Ｒ¹³は水素原子又は炭素数１〜２０の脂肪族炭化水素基であり、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、Ｙは水素原子、メチル基または炭素数６〜１２の芳香族炭化水素基、ｔ、ｕはそれぞれ１〜２０の整数を示す）

（式中、Ｒ¹⁴は炭素数１〜２０の脂肪族炭化水素基または炭素数６〜１２の芳香族炭化水素基、Ｒ¹⁵は水素原子又は炭素数１〜２０の脂肪族炭化水素基であり、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、ｗは１〜２０の整数を示す）
で表されるリン含有化合物よりなる群から選択される少なくとも１種であり、（ｂ２）成分が、一般式（１３）〜（１７）： More preferably, the component (b1) is represented by the general formulas (7) to (12):

(In the formula, R ⁵ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, R ⁶ and R ⁷ are hydrogen atoms or an aliphatic hydrocarbon having 1 to 20 carbon atoms. Group, p represents an integer of 1 to 11.)

(In the formula, R ⁸ 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 ⁹ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and 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, and r represents an integer of 1 to 12.)

(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. They may be the same or different, and s represents an integer of 1 to 11)

(In the formula, R ¹³ 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. To 12 aromatic hydrocarbon groups, t and u each represent an integer of 1 to 20)

(In the formula, R ¹⁴ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ¹⁵ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. They may be the same or different, w represents an integer of 1 to 20)
And at least one selected from the group consisting of phosphorus-containing compounds represented by general formulas (13) to (17):

（式中、ｘは１〜１６の整数を示す）

（式中、Ｒ¹⁶は水素原子又は炭素数１〜２０の脂肪族炭化水素基であり、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、ｙは１〜４の整数を示す）

（式中、ｖは１〜１６の整数、ｚは１〜４の整数を示す）

（式中、Ｒ¹⁷は水素原子又は炭素数１〜２０の脂肪族炭化水素基であり、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、ｊは１〜１２の整数を示す）

（式中、Ｒ¹⁸は水素原子又は炭素数１〜２０の脂肪族炭化水素基であり、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、ｋは１〜４の整数を示す）

(Wherein x represents an integer of 1 to 16)

(In the formula, R ¹⁶ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and y represents an integer of 1 to 4)

(In the formula, v represents an integer of 1 to 16, and z represents an integer of 1 to 4)

(In the formula, R ¹⁷ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and j represents an integer of 1 to 12)

(In the formula, R ¹⁸ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and k represents an integer of 1 to 4)

It is a flame retardant polyester artificial hair that is at least one selected from the group consisting of bromine-containing compounds represented by the formula (1), and is organic with respect to 100 parts by weight of the composition comprising the components (A) and (B). Fine fibers (C) and / or inorganic fine particles (D) 0.1 to 5 parts by weight are mixed and have fine protrusions on the fiber surface, and (C) component is polyarylate, polyamide, fluororesin , Silicone resin, cross-linked acrylic resin, and cross-linked polystyrene, and (D) component is calcium carbonate, silicon oxide, titanium oxide, aluminum oxide, zinc oxide, talc, kaolin, montmorillonite, bentonite The flame retardant polyester-based artificial hair fiber, which is at least one selected from the group consisting of mica.

  The flame retardant polyester-based artificial hair fiber preferably has a single fiber fineness of 10 to 100 dtex.

  According to the present invention, polyester-based fibers that maintain the physical properties of ordinary polyester fibers such as heat resistance and high elongation, are excellent in flame retardancy, setability and drip resistance, and have a controlled gloss of the fibers are used. The obtained artificial hair is obtained.

  The flame-retardant polyester artificial hair of the present invention comprises a polyester (A) composed of at least one of polyalkylene terephthalate and a copolymerized polyester mainly composed of polyalkylene terephthalate, a monomer component (b1) whose main structural unit contains a phosphorus element. ) And / or a monomer component (b2) containing elemental bromine, and a fiber obtained by melt spinning a composition comprising a polymer flame retardant (B) copolymerized by an ester bond.

  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 poly 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, Polyesters obtained by copolymerization of dihydroxyethyl 5-sodium sulfoisophthalate, etc.) are 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.

  The polymer flame retardant (B) used in the present invention is a monomer component (b1) containing a phosphorus element as a main structural unit and / or a monomer component (b2) containing a bromine element, and is copolymerized by an ester bond. Preferably, it has a structure represented by the general formulas (1) to (3).

  There is no limitation in particular in the monomer component (b1) containing the phosphorus element used for this invention, If it is a reaction type phosphorus containing flame retardant generally used, it can be used. As a monomer component containing a phosphorus element, what has a structure represented by the said General Formula (4)-(6) is preferable. That is, an atomic group A containing a phosphorus element and two groups selected from the group consisting of a carboxyl group, an ester group, a hydroxyl group, and an ether group having ester-forming ability (even though they are the same, they are different. Compound).

  More preferable examples include phosphorus compounds represented by the general formulas (7) to (12). That is, an atomic group containing a phosphoryl group and two groups selected from the group consisting of a carboxyl group, an ester group, a hydroxyl group and an ether group having ester-forming ability (they are different even if they are the same) It is also a compound having Specific examples include, for example, diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-methacryloyloxyethyl 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:

などのリン含有化合物が挙げられる。

And phosphorus-containing compounds such as

  The monomer component (b2) containing elemental bromine used in the present invention is not particularly limited, and any compound having a copolymerizable functional group can be used. As the monomer component containing bromine element, those having structures represented by the general formulas (4) to (6) are preferable. That is, an atomic group A containing a bromine element and two groups selected from the group consisting of a carboxyl group, an ester group, a hydroxyl group, and an ether group having ester-forming ability (even though they are the same, they are different. Compound).

  More preferable examples include bromine-containing compounds represented by the general formulas (13) to (17). That is, an atomic group containing a brominated aromatic hydrocarbon and two groups selected from the group consisting of a carboxyl group, an ester group, a hydroxyl group, and an ether group having ester-forming ability (they may be the same) , Which may be different). As a specific example, for example, the formula:

などの臭素含有化合物が挙げられる。

Bromine-containing compounds such as

  The component (B) can be produced by a known method, such as a method in which a dicarboxylic acid and its derivative, a diol component and its derivative, and a component (b1) and / or (b2) are mixed and polycondensed or a thermoplastic polyester. A method in which a copolymer is obtained by depolymerizing a diol component such as ethylene glycol, mixing (b1) and / or (b2) components at the time of depolymerization, and polycondensing again is preferable. Dimethyl acid, ethylene glycol, and (b1) and / or (b2) components are mixed at a specific ratio, and a catalytic amount of antimony trioxide or germanium dioxide is added and heated to cause a transesterification reaction to produce a low molecular weight polymer. Thereafter, the reaction product can be produced by heating under reduced pressure to cause a polycondensation reaction until a desired degree of polymerization is achieved.

  The main chain structure of the component (B) is a polyester bond, and the content of the component (b1) and / or (b2) in the component (B) is preferably 60 to 95 mol%, more preferably 65 to 90 mol%. Preferably, 70 to 85 mol% is more preferable. When the content of the component (b1) and / or the component (b2) is less than 60 mol%, the content of phosphorus and / or bromine decreases, so that the flame retardancy tends to decrease, and 95 mol% is reduced. If it exceeds the upper limit, the compatibility between the component (B) and the component (A) is deteriorated, and the transparency and color developability are lowered, or the spinning processability and yarn breakage are likely to occur.

  (B) As a number average molecular weight of a component, 5000-80000 are preferable, 8000-70000 are more preferable, and it is more preferable that it is 10000-60000. When the molecular weight is less than 5,000, the heat resistance is lowered and the resulting artificial hair tends to drip when in contact with the flame. If the molecular weight exceeds 80000, the appearance and There is a tendency for the spinning processability to decrease.

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

  The average particle diameter of the component (C) and / or the component (D) is preferably 0.1 to 15 μm, more preferably 0.2 to 10 μm, and further preferably 0.5 to 8 μm. When the particle diameter is smaller than 0.1 μm, the gloss adjustment effect is small, and when the particle diameter is larger than 15 μm, the gloss adjustment effect is small or thread breakage occurs.

  Although the usage-amount of (C) and / or (D) component is not specifically limited, It is preferable that it is 0.1-5 weight part with respect to 100 weight part of compositions which consist of (A) and (B) component. 0.2 to 3 parts by weight is more preferable, and 0.3 to 2 parts by weight is further preferable. If the amount used is more than 5 parts by weight, the appearance, hue, and color developability are impaired. It will be enough.

The component (C) can be used as long as it is an organic resin component having a structure that is incompatible with the component (A) and / or the component (B) or is not partially compatible with the 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 of the unsaturated acid and a dihydric alcohol or a trihydric alcohol. Can do. Examples of the unsaturated acid include fumaric acid, maleic acid, itaconic acid, and examples of the saturated acid include phthalic acid, terephthalic acid, succinic acid, glutaric acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. It is done. 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 here include acrylic acid and derivatives of acrylic acid, such as methyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, hydroxyethyl acrylate, acrylonitrile, acrylamide, N- Methylolacrylamide, or a derivative of methacrylic acid, 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 examples of the monomer include divinylbenzene, a reaction product of glycol and methacrylic acid or acrylic acid, such as ethylene glycol dimethacrylate and neopentyl glycol dimethacrylate, but are not limited thereto. The addition amount is preferably 0.02 to 5 parts by weight with respect to 100 parts by weight of the monomer having one vinyl group. As the polymerization initiator, a peroxide radical polymerization initiator is preferable, 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 weight based on 100 parts by weight of the monomer having one vinyl group.

  As the component (D), those having a refractive index close to the refractive index of the components (A) and (B) are preferable in view of the effects on the transparency and color developability of the fiber. For example, calcium carbonate, silicon oxide, titanium oxide , Aluminum oxide, zinc oxide, talc, kaolin, montmorillonite, bentonite, mica and the like. These may be used alone or in combination of two or more. Among these, fine particles close to a spherical shape have a higher gloss adjusting effect, and composite particles mainly composed of silicon oxide or silicon oxide are preferable. (D) component used for this invention may be surface-treated with an epoxy compound, a silane compound, an isocyanate compound, a titanate compound, etc. as needed.

  The flame-retardant polyester-based composition used in the present invention can be prepared by, for example, dry blending the components (A) and (B), and further the components (C) and / or (D), followed by various general kneading. It can manufacture by melt-kneading using a machine.

  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.

  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, and the spun yarn is passed through a heating tube, cooled to a glass transition point or lower, and 50 to 5000 m / min. A spun yarn is obtained by taking up 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 undrawn yarn is heat-drawn, and the drawing may be carried out by any of a two-step method in which the undrawn yarn is wound once and then drawn, and a direct spinning drawing method in which the yarn is continuously drawn without winding. . 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 10 to 100 dtex, more preferably 20 to 90 dtex. Suitable for artificial hair. Moreover, as a fiber for 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 has self-extinguishing property.

  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 and elongation of the filament is measured using an INTESCO Model 201 model manufactured by Intesco. 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 3.4 × 10 ⁻³ N × fineness (dtex), a tensile speed of 20 mm / min, and the high elongation is measured. The test is repeated 10 times under the same conditions, and the average value is defined as the filament elongation.

(Flame retardance)
A filament having a fineness of about 50 dtex is cut into a length of 150 mm, 0.7 g is bundled, and one end is clamped and fixed to a stand, and hung vertically. Evaluation was performed by indirectly burning a 20 mm flame on a fixed filament having an effective length of 120 mm for 3 seconds and burning it.
-Flammability-
A: After flame time is 0 seconds (no ignition)
○: Less than 3 seconds Δ: 3 to 10
X: 10 seconds or more -Drip resistance-
A: Drip number is 0
○: 5 or less Δ: 6 to 10
×: 11 or more

(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 gets 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 pulling out are visually evaluated.
-Fusion-
○: None.
Δ: Slightly present.
X: Yes.
-Crimp / Thread breakage-
○: None.
Δ: Slightly present.
X: Yes.
-Rod out-
○: The iron rod comes out without resistance.
Δ: There is some resistance.
X: There is resistance and it is hard to come off.
-Setability-
○: The set is easy to attach and the curl is stable.
Δ: The set is cheap, but the curl is slightly broken.
X: The set is difficult to attach or the curl is broken.

  Next, Production Examples 1 to 5 of the component (B) used in this example are shown.

(Production Example 1)
582 g of dimethyl terephthalate, 1368 g of ethylene glycol and 0.79 g of calcium acetate monohydrate are charged into a transesterification can and heated up from 140 ° C. to 230 ° C. over 4 hours in a nitrogen gas atmosphere. The ester exchange reaction was carried out while distilling. Furthermore, the following phosphorus-containing monomer 1;

After adding 1470 g, it was made to react at 250 degreeC. Subsequently, 2.91 g of trimethyl phosphate and 1.75 g of calcium acetate monohydrate were reacted in 50 g of ethylene glycol for 60 minutes at 120 ° C. under total reflux. 0.75 g of salt was dissolved and transferred to a polymerization can with 0.53 parts of antimony trioxide. Subsequently, the pressure was reduced from 760 mmHg to 30 mmHg over 1 hour, and at the same time, the temperature was raised from 230 ° C. to 285 ° C. over 1 hour 30 minutes. Under a reduced pressure of 1 mmHg or less, polycondensation was continued for 3 hours at a polymerization temperature of 285 ° C. to obtain a polymer flame retardant 1.

を１７３６ｇとした以外は、製造例１と同様にして、高分子難燃剤２を得た。 (Production Example 2)
970 g of dimethyl terephthalate, 1804 g of ethylene glycol, the following phosphorus-containing monomer 2;

The flame retardant 2 was obtained in the same manner as in Production Example 1, except that 1736 g was used.

(Production Example 3)
960 g of polyethylene terephthalate, 2547 g of ethylene glycol, the following bromine-containing monomer 1;

2860 g and antimony trioxide 0.38 g were charged into a transesterification can and heated from 140 ° C. to 230 ° C. over 4 hours in a nitrogen gas atmosphere to perform depolymerization and transesterification. Subsequently, the pressure was reduced from 760 mmHg to 30 mmHg over 1 hour, and at the same time, the temperature was raised from 230 ° C. to 285 ° C. over 1 hour 30 minutes. Under a reduced pressure of 1 mmHg or less, polycondensation was continued for 3 hours at a polymerization temperature of 285 ° C. to obtain a polymer flame retardant 3.

を１７８５ｇとした以外は、製造例１と同様にして、高分子難燃剤４を得た。 (Production Example 4)
291 g of dimethyl terephthalate, 1384 g of ethylene glycol, the following bromine-containing monomer 2;

The flame retardant 4 was obtained in the same manner as in Production Example 1 except that 1785 g was used.

(Production Example 5)
Polymer flame retardant 5 was obtained in the same manner as in Production Example 1, except that 970 g of dimethyl terephthalate, 822 g of ethylene glycol, and 217 g of phosphorus-containing monomer 2 were used.

(Examples 1-8)
Polyethylene terephthalate, polymer flame retardant, organic fine particles and inorganic fine particles dried to a water content of 100 ppm or less were mixed in the ratios shown in Table 1, and further colored polyester pellets PESM6100 BLACK (manufactured by Dainichi Seika Kogyo Co., Ltd., carbon) 2 parts of black content was added and dry blended, supplied to a twin screw extruder, melt-kneaded at 280 ° C., pelletized, and dried to a water 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：ポリエチレンテレフタレート、固有粘度ＩＶ＝０．８５、カネボウ合繊（株）製
＊２：架橋アクリル粒子、平均粒子径１．８μｍ、綜研化学（株）製
＊３：球状微粉末シリカ、平均粒子径４μｍ、富士シリシア（株）製

* 1: Polyethylene terephthalate, intrinsic viscosity IV = 0.85, manufactured by Kanebo Gosei Co., Ltd. * 2: Cross-linked acrylic particles, average particle size 1.8 μm, manufactured by Soken Chemical Co., Ltd. * 3: Spherical fine powder silica, average particles 4μm in diameter, manufactured by Fuji Silysia Co., Ltd.

  Table 2 shows the results of evaluation of iron setability using the obtained fibers, with regard to high elongation, flame retardancy, gloss, touch, comb.

(Comparative Examples 1-5)
Polyethylene terephthalate and a flame retardant were mixed in the ratios shown in Table 3, and polyester fibers (multifilament) having a single fiber fineness of about 50 dtex were obtained in the same manner as in the Examples.

＊１：ポリエチレンテレフタレート、固有粘度ＩＶ＝０．８５、カネボウ合繊（株）製
＊４：縮合リン酸エステル系難燃剤、大八化学工業（株）製
＊５：リン共重合型難燃ポリエステル樹脂、東洋紡績（株）製

* 1: Polyethylene terephthalate, intrinsic viscosity IV = 0.85, manufactured by Kanebo Gosei Co., Ltd. * 4: Condensed phosphate ester flame retardant, manufactured by Daihachi Chemical Industry Co., Ltd. * 5: Phosphorus copolymer type flame retardant polyester resin Manufactured by Toyobo Co., Ltd.

  Table 4 shows the results of evaluation of iron setability using the obtained fibers, with regard to high elongation, flame retardancy, gloss, touch, comb.

As shown in Tables 2 and 4, in contrast to the comparative examples, in the examples, the main structural unit is a phosphorus-containing monomer and / or bromine-containing monomer, and a polymer flame retardant copolymerized by an ester bond is used. As a result, it was confirmed that there was no decrease in spinning processability, transparency, tactile sensation, iron setability, etc., and excellent flame retardancy. Therefore, the fiber for artificial hair using the composition containing the polymer flame retardant according to the present invention has a spinning processability and transparency while maintaining the mechanical properties and thermal properties of polyester as compared with conventional fibers for artificial hair. It was confirmed that the properties, tactile sensation, setability, and flame retardancy were improved, and it was possible to use them effectively as artificial hair.

Claims (12)

  For 100 parts by weight of the polyester (A) comprising at least one polyalkylene terephthalate and a copolymer polyester mainly composed of polyalkylene terephthalate, the main constituent unit is a monomer component (b1) containing a phosphorus element and / or a bromine element. Flame retardant polyester artificial hair formed from a composition obtained by melt-kneading 5 to 50 parts by weight of a polymer flame retardant (B) which is a monomer component (b2) and is copolymerized by an ester bond .   The flame-retardant polyester artificial hair according to claim 1, wherein the component (A) is at least one polymer selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate. The flame-retardant polyester artificial hair according to claim 1, wherein the component (B) has a structure represented by the following general formulas (1) to (3).

(In the formula, R ¹ is an aliphatic hydrocarbon group including a straight chain or branched chain having 2 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ² is an aromatic hydrocarbon group having 6 to 12 carbon atoms. Group A is an atomic group containing phosphorus element or bromine element, m / n = 60/40 to 95/5.)   The flame-retardant polyester artificial hair according to claim 1 or 3, wherein the component (B) has a number average molecular weight of 5000 to 80000.   The flame-retardant polyester artificial hair according to any one of claims 1, 3, and 4, wherein the content of the component (b1) and / or the component (b2) in the component (B) is 60 to 95 mol%. The flame-retardant polyester artificial hair according to any one of claims 1, 3, 4, and 5, wherein the component (b1) and the component (b2) have a structure represented by the following general formulas (4) to (6). .

Wherein R ³ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, R ⁴ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, (A may be different, and A represents an atomic group containing phosphorus element or bromine element.) The component (b1) is represented by the general formulas (7) to (12):

(In the formula, R ⁵ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, R ⁶ and R ⁷ are hydrogen atoms or an aliphatic hydrocarbon having 1 to 20 carbon atoms. Group, p represents an integer of 1 to 11.)

(In the formula, R ⁸ 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 ⁹ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and 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, and r represents an integer of 1 to 12.)

(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. They may be the same or different, and s represents an integer of 1 to 11)

(In the formula, R ¹³ 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. To 12 aromatic hydrocarbon groups, t and u each represent an integer of 1 to 20)

(In the formula, R ¹⁴ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ¹⁵ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. They may be the same or different, w represents an integer of 1 to 20)
The flame-retardant polyester-based artificial hair according to any one of claims 1, 3, 4, and 5, which is at least one selected from the group consisting of phosphorus-containing compounds represented by the formula: The component (b2) is represented by the general formulas (13) to (17):

(Wherein x represents an integer of 1 to 16)

(In the formula, R ¹⁶ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and y represents an integer of 1 to 4)

(In the formula, v represents an integer of 1 to 16, and z represents an integer of 1 to 4)

(In the formula, R ¹⁷ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and j represents an integer of 1 to 12)

(In the formula, R ¹⁸ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and k represents an integer of 1 to 4)
The flame-retardant polyester-based artificial hair according to any one of claims 1, 3, 4, and 5, which is at least one selected from the group consisting of bromine-containing compounds represented by:   Fine protrusions on the fiber surface in which 0.1 to 5 parts by weight of organic fine particles (C) and / or inorganic fine particles (D) are mixed with 100 parts by weight of the composition comprising the components (A) and (B). The flame-retardant polyester artificial hair according to any one of claims 1 to 8.   The flame-retardant polyester artificial hair according to claim 9, wherein the component (C) is at least one selected from the group consisting of polyarylate, polyamide, fluororesin, silicone resin, crosslinked acrylic resin, and crosslinked polystyrene.   The component (D) is at least one selected from the group consisting of calcium carbonate, silicon oxide, titanium oxide, aluminum oxide, zinc oxide, talc, kaolin, montmorillonite, bentonite, mica, and silica-melamine composite particles. 9. The flame-retardant polyester artificial hair according to 9. The flame-retardant polyester artificial hair according to any one of claims 1 to 11, wherein the single fiber fineness is 10 to 100 dtex.