JP2007131982A - Flame-retardant polyester-based artificial hair - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polyester-based artificial hair that keeps fiber properties such as heat resistance, strength elongation, etc., of ordinary polyester fiber and has excellent setting properties, feel and combing property and high flame retardance. <P>SOLUTION: The flame-retardant polyester-based artificial fiber is obtained by subjecting a composition comprising a polyester, a brominated epoxy-based flame retardant having the ratio a/b of the epoxy equivalent (a) to the number-average molecular weight (b) of ≥1 and an antimony compound to melt spinning so as to control occurrence of gel during spinning, to keep excellent spinning stability and has fiber properties such as heat resistance, strength elongation, etc., of ordinary polyester fiber and to have excellent setting properties, feel and combing property. <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 brominated epoxy flame retardant and an antimony compound. More specifically, the present invention relates to a flame-retardant polyester artificial hair that suppresses thickening during melt spinning, maintains fiber properties such as heat resistance and high elongation, and has excellent setability, tactile sensation, and transparency. .

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 conventional polyester fibers are flammable, various attempts have been made to improve the flame retardancy of polyester fibers. 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 cost.

  In addition, when a flame retardant having reactivity such as a brominated epoxy flame retardant is used for the polyester, a flame retardant having insufficient thermal stability, an antimony compound, etc. There remains a problem that a reaction occurs between the flame retardants, which tends to increase the viscosity or gelation, causing breakage during melt spinning and causing nozzle clogging.

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

  The present invention solves the conventional problems as described above, suppresses thickening during melt spinning processing, maintains the physical properties of fibers such as heat resistance and high elongation of ordinary polyester fibers, and is easy to set, feel and comb. An object of the present invention is to provide a polyester-based artificial hair that is excellent in resistance and has high flame retardancy.

  As a result of intensive studies in order to solve the above problems, the present inventors have melt-spun a composition comprising a specific brominated epoxy flame retardant and an antimony compound in a polyester. Suppressing thickening at the time, maintaining the physical properties of fibers such as heat resistance and high elongation of ordinary polyester fibers, and found that flame retardant polyester artificial hair excellent in setability, touch, and transparency can be obtained, The present invention has been completed.

  That is, the present invention provides an epoxy equivalent (a) and a number average molecular weight (b) 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. A polyester-based artificial material formed from a composition comprising 5 to 30 parts by weight of a brominated epoxy flame retardant (B) having a ratio a / b of 1 or more and 0.5 to 10 parts by weight of an antimony compound (C) Hair, preferably polyester (A) is at least one polymer selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate, polyester-based artificial hair, brominated epoxy flame retardant (B) ) Is a number average molecular weight of 50000 or less, more preferably The polyester-based artificial hair having a number average molecular weight of 30000 or less and a ratio a / b of epoxy equivalent (a) to number average molecular weight (b) of 2 or more, the antimony compound (C) component is antimony trioxide And antimony tetroxide, antimony pentoxide, and sodium antimonate. The polyester artificial hair is at least one antimony compound selected from the group consisting of sodium antimonate.

  Furthermore, the polyester artificial hair containing 0.1 to 5 parts by weight of organic fine particles (D) and / or inorganic fine particles (E) with respect to 100 parts by weight of polyester (A), more preferably organic fine particles (D) Is at least one selected from the group consisting of polyarylate, polyamide, fluororesin, silicone resin, cross-linked acrylic resin and cross-linked polystyrene, and the above-mentioned polyester-based artificial hair, inorganic fine particles (E) are calcium carbonate, silicon oxide, The present invention relates to the above-mentioned polyester-based artificial hair which is at least one selected from the group consisting of a silica / melamine resin composite, titanium oxide, aluminum oxide, zinc oxide, talc, kaolin, montmorillonite, bentonite and mica.

  According to the present invention, the thickening at the time of melt spinning processing is suppressed, the physical properties of fibers such as heat resistance and high elongation of ordinary polyester fibers are maintained, the setability, tactile sensation, combing are excellent, and high flame retardancy is achieved. Polyester artificial hair is obtained.

  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) and an antimony compound (C ). A fiber obtained by melt spinning a composition comprising

  The polyalkylene terephthalate contained in the polyester (A) used in the present invention or a copolymerized polyester mainly composed of polyalkylene terephthalate, for example, polyalkylene terephthalate such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and / or Examples thereof include copolymer polyesters mainly composed of these polyalkylene terephthalates and containing a small amount of a copolymer component. As the polyalkylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate are particularly preferable from the viewpoint of availability and cost.

  The main component 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, copolymerized polyester (polyester mainly composed of polyethylene terephthalate and copolymerized with ethylene glycol ether of bisphenol A, polyester copolymerized with 1,4-cyclohexanedimethanol, Polyester copolymerized with dihydroxyethyl 5-sodiumsulfoisophthalate) is preferred, and those in which two or more of these are mixed are also preferred.

  The intrinsic viscosity of 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.

  In the present invention, by using the brominated epoxy flame retardant (B) in which the ratio a / b between the epoxy equivalent (a) and the number average molecular weight (b) is in a specific range, Gel generation can be suppressed, trouble during spinning such as yarn breakage can be reduced, spinning stability can be improved, and a filament having good yarn properties can be obtained.

  That is, the cause of gel generation is not clear, but in the presence of the antimony compound (C), the reaction derived from the terminal carboxylic acid of the polyester is accelerated. Especially when a brominated epoxy flame retardant is used, Due to the reaction between the carboxylic acid terminal and the epoxy group in combination with the heating, the partially brominated epoxy flame retardant is reacted with the carboxylic acid terminal of the polyester and the epoxy group during the melt-kneading and melt spinning. The present inventors speculate that gelation may occur due to thickening due to partial molecular weight increase of the polyester.

  Therefore, by specifying the ratio a / b of the epoxy equivalent (a) and the number average molecular weight (b) of the brominated epoxy flame retardant (B), the sealing ratio of the terminal epoxy group can be increased, As the brominated epoxy flame retardant (B) in the present invention, the ratio a / b between the epoxy equivalent (a) and the number average molecular weight (b) is preferably 1 or more, and more preferably 2 or more. .

  The number average molecular weight of the brominated epoxy flame retardant (B) in the present invention is preferably 50000 or less, and more preferably 30000 or less.

  In the presence of an antimony compound, the brominated epoxy flame retardant causes a thickening due to an increase in the molecular weight of the polyester due to the reaction between the carboxylic acid terminal of the polyester and the epoxy group during melt kneading and melt spinning. These lead to a decrease in spinnability and a deterioration in yarn properties. When a / b is less than 1, in the brominated epoxy flame retardant, the proportion of molecules having an epoxy group at both ends increases, and the viscosity tends to increase due to the reaction between the epoxy group and the carboxylic acid end. . When a / b is 1 or more, the ratio of those having 1 or less epoxy ends in the brominated epoxy flame retardant molecule is high, and even when reacted, the increase in molecular weight is small and the viscosity is difficult to increase. However, even when a / b is 1 or more, if the number average molecular weight of the brominated epoxy flame retardant exceeds 50000, the viscosity may increase due to an increase in molecular weight.

  The epoxy equivalent (a) is a value measured by a method according to JIS K7236, and the number average molecular weight (b) is a value measured by a gel permeation chromatograph (GPC) method.

The amount of the brominated epoxy flame retardant (B) used in the present invention is preferably 5 to 30 parts by weight, more preferably 6 to 25 parts by weight, and 7 to 20 parts by weight with respect to 100 parts by weight of the polyester (A). Further preferred. When the amount of the bromine-containing flame retardant (B) used is less than 5 parts by weight, the flame retardant effect tends to be difficult to obtain, and when it exceeds 30 parts by weight, the mechanical properties, heat resistance, and drip resistance of the resulting fiber are reduced. In the present invention, flame retardancy is expressed by blending the brominated epoxy flame retardant (B), but the flame retardancy effect is remarkably improved by blending the antimony compound (C).

  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. Of these, sodium antimonate is preferred 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.

  The amount of antimony compound (C) used in the present invention is preferably 0.5 to 10 parts by weight, more preferably 0.6 to 9 parts by weight, and 0.7 to 7 parts by weight per 100 parts by weight of component (A). Part is more preferable. When the amount of the antimony compound (C) used is less than 0.5 parts by weight, the improvement of the flame retardancy tends to be small, and when it exceeds 10 parts by weight, the processing stability, appearance, and transparency tend to be impaired. is there.

  The fiber for flame-retardant polyester-based artificial hair of the present invention is formed by mixing fine organic particles (D) and / or inorganic fine particles (E) to form fine protrusions on the surface of the obtained fiber, The gloss can be adjusted.

The organic fine particles (D) in the present invention can be used as long as they are organic resins having a structure that is not compatible with or partially compatible 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 acid include fumaric acid, maleic acid, and itaconic acid. Examples of the saturated acid include phthalic acid, terephthalic acid, succinic acid, glutaric acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. Is 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 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 with respect to 100 parts by weight of the monomer having one vinyl group.

  As the inorganic fine particles (E) 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 spherical shape have a higher gloss adjusting effect, and composite particles mainly composed of silicon oxide and silicon oxide are preferable. The inorganic fine particles (E) 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 polyester-based artificial hair obtained by the present invention is prepared by, for example, drying polyester (A), brominated epoxy flame retardant (B), antimony compound (C), and organic fine particles (D) or inorganic fine particles (E). After blending, the polyester composition obtained by melt kneading using various general kneaders 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 the extruder, gear pump, base, etc. is set to 270 to 310 ° C., melt-spun, and the spun yarn is heated. After passing through the tube, the yarn is cooled 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.

  A composition obtained by dry blending polyester (A), brominated epoxy flame retardant (B) and antimony compound (C), and organic fine particles (D) or inorganic fine particles (E), a gear pump and a spinning nozzle Using a twin screw extruder or a single screw extruder using a screw having kneading ability, it can be obtained by melt spinning without taking out the resin composition once.

  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. Any of the methods may be used. 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.

  The characteristic value measurement method is as follows.

(Spinning workability)
The spun yarn obtained from the melt spinning machine is continuously taken up and visually evaluated for the presence of yarn breakage.
○: No thread breakage for more than 1 hour △: No more than 10 thread breaks per hour ×: Thread breakage occurs frequently and cannot be taken up

(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.

(Foreign substance evaluation)
The presence or absence of foreign matter (due to gel generation) in the tow filament having a length of 100 cm and a total fineness of 1 million dtex is visually evaluated.
A: No foreign matter having a diameter of 2 mm or more is observed. ○: Less than 5 foreign matters having a diameter of 2 mm or more are observed. Δ: 5 to 9 foreign matters having a diameter of 2 mm or more are observed. 10 or more observed

(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. An evaluation is made 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

(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. Stop the end with adhesive tape so that the total length is 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.
-Fusion between filaments-
○: No fusing △: Slight fusing ×: Fusing-Crimp / Thread breakage-
○: No shrinkage or thread breakage △: Slightly shrinkage or thread breakage ×: Crimping or thread breakage-Rod out-
○: The iron rod comes off smoothly. △: The iron rod is hard to come off slightly.
○: The shape of the curl is maintained Δ: The shape of the curl is slightly broken ×: The shape of the curl is broken

The raw materials used in the examples and comparative examples are as follows.
Polyester (A):
・ Polyethylene terephthalate, manufactured by Mitsubishi Chemical Corporation, BK-2180
Brominated epoxy flame retardant (B):
Brominated epoxy flame retardant, manufactured by Tohto Kasei Co., Ltd., YPB-43M, epoxy equivalent 4000, number average molecular weight 32000
-Brominated epoxy flame retardant, manufactured by Sakamoto Pharmaceutical Co., Ltd., SR-T3040, epoxy equivalent 30000, number average molecular weight 6000
-Brominated epoxy flame retardant, manufactured by Sakamoto Pharmaceutical Co., Ltd., SR-T7040, epoxy equivalent 40000, number average molecular weight 140000
Brominated epoxy flame retardant, Sakamoto Pharmaceutical Co., Ltd., SR-T5000, epoxy equivalent 5000, number average molecular weight 10,000
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
Inorganic fine particles (F):
・ Fine silica, Fuji Silysia Chemical Co., Ltd., Silicia 310, average particle size (primary particle) 2.7 μm
Pigment:
-Pigment master batch, carbon black 20wt%, manufactured by Dainichi Seika Kogyo Co., Ltd., PESM22367BLACK

(Examples 1-6)
A composition having a blending ratio shown in Table 1 is dried to a water content of 100 ppm or less, dry blended, supplied to a twin screw extruder (manufactured by Nippon Steel Works, TEX44), and melt kneaded at a barrel set temperature of 280 ° C. And pelletized, and then dried to a moisture content of 100 ppm or less. Next, using a melt spinning machine (manufactured by Shinko Machinery Co., Ltd., SV30), the molten polymer is discharged from a spinneret having a vertical cross-section nozzle hole with a barrel setting temperature of 280 ° C. and an aspect ratio of 1.4: 1, Air-cooled with 20 ° C. cooling air 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. KWC-Q (Ethoxide / Propylene Oxide Random Copolyether; manufactured by Maruhishi Oil Chemical Co., Ltd.) / Processing Agent 29 (Cationic Surfactant; Hydrophilic Fiber Treatment Agent) An aqueous solution containing 0.80% of each pure component was prepared so that the ratio was 0.20 / 0.20% omf, and a tow filament having a total fineness of 100,000 dtex was added to the tow filament. The solution was adhered so that the liquid content was 25% based on the weight, and dried at 120 ° C. for 10 minutes with a hot air dryer.

  Table 2 shows the results of evaluating the gel generation state, the strength elongation, the tactile sensation, the comb, the flame retardancy, and the iron set property using the obtained fibers.

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

  Table 2 shows the results of evaluating the gel generation state, the strength elongation, the tactile sensation, the comb, the flame retardancy, and the iron set property using the obtained fibers.

  As shown in Table 2, with respect to the comparative example, in the example, the brominated epoxy flame retardant (B) in which the ratio a / b between the epoxy equivalent (a) and the number average molecular weight (b) is 1 or more is used. By using it, it is possible to suppress thickening during melt-kneading and melt-spinning, and to reduce trouble during spinning such as yarn breakage, thereby improving spinning stability and further increasing the viscosity on the fiber surface. It was confirmed that there was no formation of protrusions derived from the material, and the tactile sensation and combing were good, the iron setability was not lowered, and high flame retardancy was exhibited. Therefore, the fiber for artificial hair using the composition of this time, compared with the fiber for conventional artificial hair, maintains the spinning stability, the mechanical properties and the thermal properties of polyester, and feels, combs, setability, difficulty. It was confirmed that it can be effectively used as artificial hair with improved flammability.

Claims (9)

The ratio a / b between the epoxy equivalent (a) and the number average molecular weight (b) is 1 with respect to 100 parts by weight of the polyester (A) comprising at least one polyalkylene terephthalate and a copolymer polyester mainly composed of polyalkylene terephthalate. Flame retardant polyester artificial hair formed from a composition comprising 5 to 30 parts by weight of the brominated epoxy flame retardant (B) and 0.5 to 10 parts by weight of the antimony compound (C).   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 flame retardant polyester artificial hair according to claim 1 or 2, wherein the brominated epoxy flame retardant (B) has a number average molecular weight of 50,000 or less. The flame-retardant polyester artificial hair according to claim 1, wherein the brominated epoxy flame retardant (B) has a number average molecular weight of 30000 or less. The flame-retardant polyester artificial hair according to claim 1, wherein the ratio a / b between the epoxy equivalent (a) and the number average molecular weight (b) of the brominated epoxy flame retardant (B) is 2 or more.   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, according to any one of claims 1 to 5. Flame retardant polyester artificial hair.   Furthermore, the flame retardance in any one of Claims 1-6 which contains 0.1-5 weight part of organic fine particles (D) and / or inorganic fine particles (E) with respect to 100 weight part of polyester (A). Polyester artificial hair.   The flame-retardant polyester artificial hair according to claim 7, wherein the organic fine particles (D) are at least one selected from the group consisting of polyarylate, polyamide, fluororesin, silicone resin, crosslinked acrylic resin and crosslinked polystyrene.   The inorganic fine particles (E) are at least one selected from the group consisting of calcium carbonate, silicon oxide, silica / melamine resin composite, titanium oxide, aluminum oxide, zinc oxide, talc, kaolin, montmorillonite, bentonite and mica. The flame-retardant polyester artificial hair according to claim 7.