JP2006118068A - Flame-retardant polyester-based artificial hair - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant polyester-based artificial hair having excellent setting properties, touch feeling, gloss, transparency and processing stability, and having high flame retardance while keeping the fiber properties such as heat resistance, strength and elongation of a normal polyester fiber. <P>SOLUTION: The flame-retardant polyester-based artificial hair having the above-mentional various properties is obtained by melt-spinning a composition containing a bromine-containing flame retardant, zinc borate and/or zinc stannate, preferably, a composition containing organic fine particles and/or inorganic fine particles besides them. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a flame retardant formed from a composition comprising a polyester containing a bromine-containing flame retardant, zinc borate and / or zinc stannate, and further comprising organic fine particles and / or inorganic fine particles. The present invention relates to polyester-based artificial hair. More specifically, the present invention relates to a flame-retardant polyester artificial hair that maintains fiber properties such as heat resistance and high elongation, and is excellent in setability, touch, transparency, and processing stability.

  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 fibers using fibers mainly composed of polyester typified by polyethylene terephthalate having excellent heat resistance have been proposed. However, when used as an artificial hair material, it is necessary to impart flame retardancy from the viewpoint of safety. Since the conventional polyester fiber is flammable, various attempts have been made to improve the flame retardancy of the polyester fiber. For example, a polyester fiber obtained by copolymerizing a flame retardant monomer containing a phosphorus atom has been used. A method of forming a fiber, a method of incorporating a flame retardant into polyester fiber, and the like 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. For example, a polyester fiber obtained by copolymerizing a phosphorus compound has been proposed as an application of the flame retardant technology to artificial hair (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 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), and the like. Proposed. In the method of adding a flame retardant to the polyester fiber, in order to obtain sufficient flame resistance, it is necessary to increase the content treatment temperature to 150 ° C. or higher or to increase the content treatment time. Or a large amount of a flame retardant has to be used, causing problems such as a decrease in fiber properties, a decrease in productivity, and an increase in manufacturing costs.

  In addition, it has been proposed to improve the flame retardancy by adding an antimony compound as a flame retardant aid (Patent Documents 7 and 8). Stabilization and thread breakage due to antimony particles occur.

Thus, the actual condition is that an artificial hair that maintains the fiber properties such as heat resistance and strong elongation of the conventional polyester fiber and is excellent in setability and flame retardancy has not been obtained yet.
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 Japanese Patent No. 2693331 JP 2002-128998 A

  The present invention solves the conventional problems as described above, maintains the fiber physical properties such as heat resistance and high elongation of ordinary polyester fiber, is excellent in setability, touch, gloss, transparency, processing stability, and high difficulty. It aims at providing the polyester-type artificial hair which has a flame retardance.

As a result of intensive studies to solve the above problems, the present inventors have found that a composition comprising a bromine-containing flame retardant, zinc borate and / or zinc stannate in polyester, organic fine particles and / or Or by melt spinning a composition comprising inorganic fine particles, the fiber properties such as heat resistance and high elongation of ordinary polyester fiber are maintained, and the set property, tactile sensation, gloss, transparency, and processing stability are excellent. The present inventors have found that a flame-retardant polyester artificial hair can be obtained and have completed the present invention.
That is, the present invention relates to a bromine-containing flame retardant (B) 5 to 30 parts by weight with respect to 100 parts by weight of a polyester (A) composed of at least one of a polyalkylene terephthalate and a copolyester mainly composed of polyalkylene terephthalate. It is a polyester-based artificial hair formed from a composition obtained by melt-kneading 0.5 to 10 parts by weight of zinc oxide and / or zinc stannate (C). Preferably, component (A) is polyethylene terephthalate, Polyester artificial hair which is at least one polymer selected from the group consisting of polypropylene terephthalate and polybutylene terephthalate, (B) component is brominated aromatic flame retardant, bromine-containing phosphate ester flame retardant, bromine Polystyrene flame retardant, brominated benzyl acrylate flame retardant, brominated petroleum At least one compound selected from the group consisting of a xy 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. The polyester-based artificial hair, and the component (D) is at least one selected from the group consisting of polyarylate, polyamide, fluororesin, silicone resin, cross-linked acrylic resin, and cross-linked polystyrene Artificial hair, (E) It is related with the said polyester whose component is at least 1 sort (s) chosen from the group which consists of calcium carbonate, silicon oxide, titanium oxide, aluminum oxide, zinc oxide, talc, kaolin, montmorillonite, bentonite, and mica.

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

  Conventionally, the particle size of antimony compounds used as flame retardant aids, such as antimony trioxide, is widely about 0.5 to 1 μm in terms of dispersibility, flame retardancy uniformity, availability, etc. Have been used. However, when antimony trioxide is used as a flame retardant aid for polyester fiber, the refractive index of polyester fiber is 1.72 in the fiber axis direction and 1.54 in the direction perpendicular to the fiber axis, whereas trioxide is Since the refractive index of antimony is 2.09 to 2.29, the transparency tends to decrease. Antimony trioxide has a strong hiding power in the range of 0.4 to 1.5 μm, and when antimony trioxide in this range is used, the hue of the resulting filament tends to be lowered (whitened).

  The zinc borate and zinc stannate used in the present invention have a refractive index of 1.58 and 1.90, respectively, and are close to the refractive index of the polyester fiber, so that the transparency and hue decrease are small.

  According to the present invention, it is possible to obtain polyester-based artificial hair that maintains the physical properties of ordinary polyester fibers such as heat resistance and high elongation, is excellent in setability, touch, gloss, and transparency and has high flame retardancy.

  The flame-retardant polyester artificial hair of the present invention comprises a polyalkylene terephthalate and a polyester (A) comprising at least one copolymer polyester mainly composed of polyalkylene terephthalate, a bromine-containing flame retardant (B), zinc borate and / or Alternatively, a fiber obtained by melt spinning a composition containing zinc stannate (C) and a composition containing organic fine particles (D) and / or inorganic fine particles (E).

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

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

（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、Ｒ¹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、Ｒ²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）
これらの中では、臭素含有リン酸エステル系難燃剤、臭素化ポリスチレン系難燃剤、臭素化ベンジルアクリレート系難燃剤、臭素化エポキシ系難燃剤、臭素化フェノキシ樹脂系難燃剤、臭素化ポリカーボネート系難燃剤、テトラブロモビスフェノールＡ誘導体、臭素含有トリアジン系化合物、臭素含有イソシアヌル酸系化合物が好ましく、臭素含有リン酸エステル系難燃剤、臭素化エポキシ系難燃剤、臭素化フェノキシ樹脂系難燃剤がさらに好ましい。

(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)
Among these, bromine-containing phosphate ester flame retardant, brominated polystyrene flame retardant, brominated benzyl acrylate flame retardant, brominated epoxy flame retardant, brominated phenoxy resin flame retardant, brominated polycarbonate flame retardant , Tetrabromobisphenol A derivatives, bromine-containing triazine compounds, and bromine-containing isocyanuric acid compounds are preferred, and bromine-containing phosphate ester flame retardants, brominated epoxy flame retardants, and brominated phenoxy resin flame retardants are more preferred.

  The amount of component (B) used is preferably 5 to 30 parts by weight, more preferably 6 to 25 parts by weight, and even more preferably 7 to 20 parts by weight with respect to 100 parts by weight of component (A). If the amount used is less than 5 parts by weight, the flame retardant effect is insufficient, and if it is more than 30 parts by weight, the mechanical properties, heat resistance and drip resistance are impaired.

  (B) Although flame retardance is expressed by mix | blending a component, when using a silicon-type fiber processing agent or mixing and using with a combustible fiber, it will come to obtain sufficient flame retardance. However, the flame retardant effect is remarkably improved by blending the component (C), and sufficient flame retardancy can be obtained.

  The amount of zinc borate and / or zinc stannate (C) used in the present invention is preferably 0.5 to 10 parts by weight, and 0.6 to 9 parts by weight per 100 parts by weight of component (A). More preferred is 0.7-8 parts by weight. When the amount used is less than 0.5 parts by weight, the improvement of the flame retardancy is small, and when it is more than 10 parts by weight, the processing stability is impaired.

  (C) Although the thing of the particle diameter generally used can be used for the average particle diameter of component, 1-10 micrometers is preferable, 1.5-8 micrometers is more preferable, and 2-6 micrometers is further more preferable. Moreover, you may surface-treat with an epoxy compound, a silane compound, an isocyanate compound, a titanate compound etc. as needed.

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

  As the component (D), any organic resin component having a structure that is not compatible or partially incompatible with the component (A), which is the main component, can be used. For example, polyarylate, polyamide, fluorine Resins, silicon resins, cross-linked acrylic resins, cross-linked 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. 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 weight based on 100 parts by weight of the monomer having one vinyl group.

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

  The flame retardant polyester-based composition used in the present invention, for example, after dry blending the components (A), (B) and (C) and the components (D) and / or (E) as necessary, It can manufacture by melt-kneading using various general kneaders.

  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 polyester-based artificial hair of the present invention can be produced by melt-spinning the polyester-based composition by a normal melt spinning method.

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

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

  The polyester-based artificial hair of the present invention may contain various additives such as heat-resistant agents, light stabilizers, fluorescent agents, antioxidants, antistatic agents, pigments, plasticizers, and lubricants as necessary. Can do. By incorporating a pigment, a primary fiber can be obtained.

  The polyester-based artificial hair of the present invention thus obtained is a non-crimp raw fiber-like fiber, and its fineness is usually 10 to 100 dtex, more preferably 20 to 90 dtex, which is suitable for artificial hair. Yes. 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.

  When the polyester-based artificial hair of the present invention is priming, it can be used as it is, but when it is not priming, it can be dyed under the same conditions as ordinary polyester-based fibers.

  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.

The characteristic value measurement method is as follows.
(Spinning workability)
Spinning workability is evaluated by touching the undrawn yarn obtained by spinning with the naked eye and by hand. ○: An undrawn yarn having good properties without yarn breakage is obtained.

      Δ: There is very little thread breakage.

X: There is a thread breakage or the thread is stuck.
(Strength and elongation)
The tensile strength / elongation of the filament is measured using INTESCO Model 201 manufactured by Intesco. A filament having a length of 40 mm is taken, 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 to measure the strength and elongation. The test is repeated 10 times under the same conditions, and the average value is defined as the filament elongation.
(transparency)
A tow filament having a length of 30 cm and a total fineness of 100,000 dtex is compared with a standard filament (tow filament having a total fineness of 100,000 dtex made of polyethylene terephthalate) by visual observation under sunlight.

○: Same level as standard filament Δ: Slightly turbid compared to standard filament ×: Clearly turbid (glossy) compared to standard filament
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 (flame retardant)
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 is 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)
○: 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 (limit oxygen index)
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 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 critical oxygen index.
(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, the fusion between filaments, 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 △: Slightly ×: Present-Crimp / Thread breakage
○: None △: Slightly ×: Available-Rod out-
○: The iron rod comes out without resistance. △: There is some resistance.
○: The set is easily attached and the curl is stable. Δ: The set is cheap and the curl is slightly broken. ×: The set is difficult to be attached or the curl is broken (Examples 1 to 10).
The compositions having the ratios shown in Tables 1 and 2 were dried to a moisture content of 100 ppm or less, and the polyester pellets for coloring PESM6100 BLACK (manufactured by Dainichi Seika Kogyo Co., Ltd., carbon black content 30%, polyester as component (A) 2 parts included) were added, dry blended, supplied to a twin screw extruder, melt-kneaded at 280 ° C., pelletized, and dried to a moisture content of 100 ppm or less. Next, using a melt spinning machine, the molten polymer is discharged from a spinneret having a round cross-section nozzle hole with a nozzle diameter of 0.5 mm at 280 ° C., and cooled in a water bath at a water temperature of 50 ° C. set at a position 30 mm below the base. The undrawn yarn was obtained by winding at a speed of 100 m / min. The obtained unstretched yarn is stretched 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.

＊１：ポリエチレンテレフタレート、カネボウ合繊（株）製
＊２：トリス（トリブロモネオペンチル）ホスフェート、大八化学工業（株）製
＊３：臭素化エポキシ系難燃剤、阪本薬品工業（株）製
＊４：臭素化ポリカーボネートオリゴマー、帝人化成（株）製
＊５：錫酸亜鉛、平均粒子径２．５μｍ、日本軽金属（株）製
＊６：無水ホウ酸亜鉛、平均粒子径３μｍ、ボラックス・ジャパン（株）製
＊７：架橋アクリル粒子、平均粒子径１．８μｍ、綜研化学（株）製
＊８：球状微粉末シリカ、平均粒子径２．７μｍ、富士シリシア（株）製
＊９：三酸化アンチモン、平均粒子径０．５μｍ、日本精鉱（株）製
得られた繊維を用いて、紡糸加工性、強伸度、透明性、触感、難燃性、アイロンセット性を評価した結果を表３、４に示す。

* 1: Polyethylene terephthalate, manufactured by Kanebo Gosei Co., Ltd. * 2: Tris (tribromoneopentyl) phosphate, manufactured by Daihachi Chemical Industry Co., Ltd. * 3: Brominated epoxy flame retardant, manufactured by Sakamoto Pharmaceutical Co., Ltd. * 4: Brominated polycarbonate oligomer, manufactured by Teijin Chemicals Ltd. * 5: Zinc stannate, average particle size 2.5 μm, manufactured by Nippon Light Metal Co., Ltd. * 6: Anhydrous zinc borate, average particle size 3 μm, Borax Japan ( * 7: Cross-linked acrylic particles, average particle size 1.8 μm, manufactured by Soken Chemical Co., Ltd. * 8: Spherical fine powder silica, average particle size 2.7 μm, manufactured by Fuji Silysia Co., Ltd. * 9: Antimony trioxide , Average particle diameter 0.5 μm, manufactured by Nippon Seiko Co., Ltd. Table 3 shows the results of evaluating spinning processability, high elongation, transparency, tactile sensation, flame retardancy, and iron setability using the obtained fibers. 4 shows.

（比較例１〜４）
表２に示す比率の組成物を、水分量１００ｐｐｍ以下に乾燥し、実施例と同様にして、単繊維繊度が５０ｄｔｅｘ前後のポリエステル系繊維（マルチフィラメント）を得た。

(Comparative Examples 1-4)
The composition having the ratio shown in Table 2 was dried to a moisture content of 100 ppm or less, and polyester fibers (multifilament) having a single fiber fineness of around 50 dtex were obtained in the same manner as in the Examples.

  Table 4 shows the results of evaluating spinning processability, high elongation, transparency, gloss, touch, flame retardancy, and iron setability using the obtained fibers.

  As shown in Tables 3 and 4, with respect to the comparative example, in the examples, the use of zinc borate and / or zinc stannate reduces the spinning processability, transparency, touch, iron setability and the like. No flame retardant was confirmed. Therefore, the fiber for artificial hair using the composition containing zinc borate and / or zinc stannate this time, while maintaining the mechanical properties and thermal properties of polyester, compared with the conventional fiber for artificial hair, is a spinning process. It has been confirmed that it can be effectively used as artificial hair with improved properties, transparency, gloss, touch, setability and flame retardancy.

Claims (7)

  5 to 30 parts by weight of bromine-containing flame retardant (B), zinc borate and / or tin with respect to 100 parts by weight of polyester (A) comprising at least one polyalkylene terephthalate and copolymerized polyester mainly composed of polyalkylene terephthalate Flame retardant polyester-based artificial hair formed from a composition obtained by melt-kneading 0.5 to 10 parts by weight of zinc acid (C).   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.   Component (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, brominated phenoxy flame retardant The flame according to claim 1 or 2, which is at least one flame retardant selected from the group consisting of a flame retardant, a brominated polycarbonate flame retardant, a tetrabromobisphenol A derivative, a bromine-containing triazine compound, and a bromine-containing isocyanuric acid compound. Flammable polyester-based artificial hair.   The composition comprising the components (A), (B), and (C) is further mixed with organic fine particles (D) and / or inorganic fine particles (E), and has fine protrusions on the fiber surface. The fiber for flame-retardant polyester-based artificial hair according to any one of the above.   The flame-retardant polyester artificial hair according to claim 4, wherein the component (D) is at least one selected from the group consisting of polyarylate, polyamide, fluororesin, silicone resin, crosslinked acrylic resin, and crosslinked polystyrene.   The flame retardant according to claim 4, wherein the component (E) is at least one selected from the group consisting of calcium carbonate, silicon oxide, titanium oxide, aluminum oxide, zinc oxide, talc, kaolin, montmorillonite, bentonite and mica. Polyester artificial hair.   The single fiber fineness is 10 to 100 dtex, The flame-retardant polyester artificial hair according to any one of claims 1 to 6.