JP2005325504A - Flame-retardant polyester artificial hair - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester artificial hair keeping the fiber properties of ordinary polyester fibers such as heat-resistance, tenacity and elongation, having excellent settability, touch and transparency, exhibiting extremely high flame-retardancy and having controlled surface gloss of the fiber. <P>SOLUTION: The flame-retardant polyester artificial hair keeping the fiber properties of conventional polyester fibers such as heat-resistance, tenacity and elongation, having excellent settability, touch and transparency, and having controlled surface gloss of the fiber is produced by the melt-spinning of a polyester composition containing one or more bromine-containing flame retardants selected from a brominated epoxide flame retardant, a brominated phenoxy resin flame retardant and a brominated phosphate flame retardant and an organic cyclic phosphorus compound and/or a phosphoric acid ester amide compound or a polyester composition containing organic fine particles and/or inorganic fine particles in addition to the above components. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a flame retardant polyester-based artificial material comprising a composition comprising a polyester containing a specific bromine-containing flame retardant and a specific phosphorus-containing flame retardant, and further comprising a composition comprising organic fine particles and / or inorganic fine particles. It relates to 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, 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. Modacrylic 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 a 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 one in which the flame retarding technique is applied 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, for example, 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). Etc. have been proposed. In the method of adding a flame retardant to the polyester fiber, in order to obtain sufficient flame resistance, it is necessary to increase the content treatment temperature to 150 ° C. or higher or to increase the content treatment time. Or a large amount of a flame retardant has to be used, causing problems such as a decrease in fiber properties, a decrease in productivity, and an increase in manufacturing costs.

  Thus, the actual condition is that an artificial hair that maintains the fiber properties such as 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, maintains the fiber properties such as heat resistance and high elongation of ordinary polyester fiber, is excellent in setability, touch and transparency, and has extremely high flame retardancy. Another object of the present invention is to provide a polyester-based artificial hair in which the gloss of the fiber surface is adjusted.

  As a result of intensive studies in order to solve the above problems, the present inventors have found that polyester has at least one of a brominated epoxy flame retardant, a brominated phenoxy resin flame retardant, and a brominated phosphate ester flame retardant. By melt spinning a bromine-containing flame retardant, a composition comprising an organic cyclic phosphorus compound and / or a phosphoric ester amide compound, and further comprising a composition comprising organic fine particles and / or inorganic fine particles, The present inventors have found that flame retardant polyester-based artificial hair excellent in setability, tactile sensation, and transparency can be obtained while maintaining fiber physical properties such as heat resistance and high elongation of ordinary polyester fibers, and have completed the present invention. .

  That is, the present invention relates to a polyester (A) comprising at least one of polyalkylene terephthalate and / or copolymerized polyester mainly composed of polyalkylene terephthalate, brominated epoxy flame retardant, brominated phenoxy resin flame retardant and brominated. 100 parts by weight of the polyester (A) comprising at least one bromine-containing flame retardant (B) of a phosphate ester flame retardant and a phosphorus compound (C) comprising an organic cyclic phosphorus compound and / or a phosphoric ester amide compound On the other hand, it relates to a flame-retardant polyester artificial hair comprising a composition obtained by melt-kneading 5 to 30 parts by weight of a mixture of the bromine-containing flame retardant (B) and the phosphorus compound (C).

  The weight ratio of the bromine-containing flame retardant (B) and the phosphorus compound (C) is preferably 90/10 to 10/90.

  The polyalkylene terephthalate is preferably at least one selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate.

  The bromine-containing flame retardant (B) is at least one selected from the group consisting of brominated epoxy flame retardants and / or brominated phenoxy resin flame retardants represented by the general formulas (1) to (4). It is preferable.

(In the formula, m represents an integer of 0 to 100.)

(In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms, n is 0 to 100, and x is an integer of 0 to 5.)

(In the formula, R ² is an alkyl group having 1 to 10 carbon atoms, p is 0 to 100, and y is an integer of 0 to 5.)

(In the formula, q represents any integer of 80 to 200.)
Bromine-containing flame retardant (B) is tris (bromoethyl) phosphate, tris (bromopropyl) phosphate, tris (dibromopropyl) phosphate, tris (bromobutyl) phosphate, tris (dibromobutyl) phosphate, tris (bromoneopentyl) phosphate, tris It is preferably at least one brominated phosphate compound selected from the group consisting of (dibromoneopentyl) phosphate and tris (tribromoneopentyl) phosphate.

  The phosphorus compound (C) is represented by the general formulas (5) to (13):

(Wherein R ¹ is a hydrogen atom or a linear or branched alkyl group, which may be the same or different, and R ² is a hydrogen atom, a linear or branched alkyl group, And represents a chain or branched hydroxyalkyl group, cycloalkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted aralkyl group.)

(Wherein R ¹ is a hydrogen atom or a linear or branched alkyl group, which may be the same or different, and R ³ is a divalent linear or branched alkylene group, Chain or branched hydroxyalkyl group, cycloalkylene group, alkylene group having ether oxygen in the main chain, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, α, α′-xylylene group, substituted- An α, α′-xylylene group, an α, α′-metaxylylene group, or a substituted-α, α′-xylylene group is shown.)

(In the formula, R ¹ is a hydrogen atom or a linear or branched alkyl group, which may be the same or different, and R ⁴ is a hydrogen atom, a linear or branched alkyl group, Represents an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group.)

Wherein R ¹ is a hydrogen atom or a linear or branched alkyl group, which may be the same or different, and R ⁵ is a divalent linear or branched alkylene group, cyclo Alkylene group, alkylene group having ether oxygen in the main chain, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, α, α′-xylylene group, substituted-α, α′-xylylene group, α, An α′-metaxylylene group or a substituted-α, α′-xylylene group is shown.)

(Wherein R ¹ is a hydrogen atom or a linear or branched alkyl group, which may be the same or different, and R ⁶ is a divalent linear or branched alkylene group, or A cycloalkylene group, R ⁷ is a hydrogen atom, or a linear or branched alkyl group, and r is any one of 1 to 5)

(In the formula, R ¹ is a hydrogen atom or a linear or branched alkyl group, which may be the same or different, and R ⁸ and R ⁹ are a hydrogen atom, a linear or branched alkyl group, respectively. A cycloalkyl group, which may be the same or different, and Y is a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or (It is an unsubstituted aralkyl group, and s represents 1 or 2.)

(Wherein R ¹ is a hydrogen atom or a linear or branched alkyl group, which may be the same or different, and R ¹⁰ is a divalent linear or branched alkylene group, A hydroxyalkyl group having a chain or a branch, a cycloalkylene group, an alkylene group having an ether oxygen in the main chain, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and X is an oxygen atom or a sulfur atom And t represents 0 or 1.)

(In the formula, R ¹¹ is a hydrogen atom or a linear or branched alkyl group, which may be the same or different, and R ¹² and R ¹³ are a hydrogen atom, a linear or branched alkyl group, respectively. A straight-chain or branched hydroxyalkyl group, a cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, each of which may be the same or different, and u is 1 Or 2 is shown.)

(In the formula, R ¹¹ is a hydrogen atom or a linear or branched alkyl group which may be the same or different, and R ¹⁴ and R ¹⁵ are divalent linear or branched alkylene. Group, a linear or branched hydroxyalkyl group, a cycloalkylene group, an alkylene group having ether oxygen in the main chain, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. Or different.)
It is preferable that it is an organic cyclic phosphorus compound and / or a phosphoric ester amide compound represented by these.

  Furthermore, it is preferable to contain organic fine particles (D) and / or inorganic fine particles (E).

  The organic fine particles (D) are preferably made of 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 selected from the group consisting of an antimony trioxide compound, an antimony pentoxide compound, sodium antimonate, calcium carbonate, silicon oxide, titanium oxide, aluminum oxide, zinc oxide, talc, kaolin, montmorillonite, bentonite, and mica. It is preferable to consist of at least one selected.

  The flame-retardant polyester artificial hair of the present invention is preferably non-crimped raw silk.

  Moreover, it is preferable that the flame-retardant polyester-based artificial hair of the present invention is pre-fabricated.

  Further, the flame-retardant polyester artificial hair of the present invention preferably has a single fiber fineness of 10 to 100 dtex.

  According to the present invention, fiber properties such as heat resistance and high elongation of ordinary polyester fibers are maintained, set properties, tactile sensation, transparency are excellent, flame retardancy is high, and the gloss of the fiber surface is further improved. An adjusted polyester-based artificial hair is obtained.

  The flame-retardant polyester artificial hair of the present invention comprises a polyalkylene terephthalate and / or a polyester (A) comprising at least one of copolyesters based on polyalkylene terephthalate, a brominated epoxy flame retardant, brominated Comprising at least one bromine-containing flame retardant (B) of a phenoxy resin flame retardant and a brominated phosphate ester flame retardant, and a phosphorus compound (C) comprising an organic cyclic phosphorus compound and / or a phosphate ester amide compound, It consists of fibers obtained by melt spinning a composition obtained by melt-kneading 5 to 30 parts by weight of a mixture of the bromine-containing flame retardant (B) and the phosphorus compound (C) with respect to 100 parts by weight of the polyester (A).

  Examples of the polyalkylene terephthalate contained in the polyester (A) used in the present invention include polyalkylene terephthalates such as polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate. Examples of the copolymer polyester mainly composed of polyalkylene terephthalate include copolymer polyesters mainly composed of these polyalkylene terephthalates and containing a small amount of copolymer components.

  Here, the main component means that the copolymerized polyester contains 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 copolymerized polyester is usually produced by reacting a polymer of terephthalic acid and / or its derivative (for example, methyl terephthalate) as a main component with an alkylene glycol containing a small amount of a copolymer component. Is preferable from the viewpoints of stability and ease of operation, but a mixture of a main component of terephthalic acid and / or a derivative thereof and an alkylene glycol further containing a monomer or oligomer component which is a copolymerization component. You may manufacture by polymerizing.

  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, And polyester obtained by copolymerization of dihydroxyethyl 5-sodium sulfoisophthalate.

  The polyalkylene terephthalate and the copolyester may be used alone or in combination of two or more. Among these, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, or the above copolymerized polyester (polyester mainly composed of polyethylene terephthalate and copolymerized with ethylene glycol ether of bisphenol A, copolymerized with 1,4-cyclohexanedimethanol. Polyesters obtained by copolymerization of dihydroxyethyl 5-sodiumsulfoisophthalate), and a mixture of two or more of these is also preferred.

  The intrinsic viscosity of the polyester (A) 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, and when it exceeds 1.4, the melt viscosity increases with increasing molecular weight, and melt spinning. Tends to be difficult and the fineness tends to be non-uniform.

  The brominated epoxy flame retardant, brominated phenoxy resin flame retardant and brominated phosphate ester flame retardant used in the present invention are not particularly limited and are generally used. Any of these can be used.

  Examples of the bromine-containing flame retardant (B) include an end-unsealed brominated epoxy flame retardant represented by the general formula (1) and a one-end blocked brominated epoxy flame retardant represented by the general formula (2). Examples thereof include a flame retardant, a both-end-capped brominated epoxy flame retardant represented by the general formula (3), and a brominated phenoxy resin flame retardant represented by the general formula (4).

  As a terminal non-blocking brominated epoxy flame retardant represented by the general formula (1), the integer m in the formula is preferably 0 to 100, and more preferably 5 to 95. Those having m greater than 100 are difficult to synthesize because they are difficult to synthesize. Specific examples of the end-unsealed brominated epoxy flame retardant represented by the general formula (1) include the following formula:

And the like.

  As the one-end-capped brominated epoxy flame retardant represented by the general formula (2), the integer n in the formula is preferably 0 to 100, and more preferably 5 to 95. Those having n over 100 are difficult to synthesize, and are difficult to obtain. Moreover, x in a formula shows either the integer of 0-5, and it is preferable that it is 1-3. Specific examples of the one-end-capped brominated epoxy flame retardant represented by the general formula (2) include the following formula:

And the like.

  As the both-end-capped brominated epoxy flame retardant represented by the general formula (3), the integer p in the formula is preferably 0 to 100, more preferably 5 to 95. Those having p of more than 100 are difficult to synthesize because of difficulty in synthesis. Moreover, y in a formula shows either the integer of 0-5, and it is preferable that it is 1-3. Specific examples of the both-end-capped brominated epoxy flame retardant represented by the general formula (3) include the following formula:

And the like.

  As a brominated phenoxy resin flame retardant represented by the general formula (4), the integer q in the formula is preferably 80 to 200, and more preferably 85 to 200. Those having q over 200 are difficult to synthesize, and are difficult to obtain. Specific examples of the brominated phenoxy resin flame retardant represented by the general formula (4) include the following formula:

And the like.

  The bromine-containing flame retardant (B) includes tris (bromoethyl) phosphate, tris (bromopropyl) phosphate, tris (dibromopropyl) phosphate, tris (bromobutyl) phosphate, tris (dibromobutyl) phosphate, tris (bromoneopentyl). Brominated phosphate ester compounds such as phosphate), tris (dibromoneopentyl) phosphate, tris (tribromoneopentyl) phosphate.

  As the bromine-containing flame retardant (B), it is possible to use both ends unblocked brominated epoxy flame retardant, brominated phenoxy resin flame retardant and brominated phosphate ester flame retardant. It is preferable from the viewpoints of touch and spinning stability.

  These may be used alone or in combination of two or more.

  In the present invention, the bromine-containing flame retardant (B) and the phosphorus compound (C) composed of an organic cyclic phosphorus compound and / or a phosphoric ester amide compound are used in combination, whereby the bromine-containing flame retardant or the phosphorus-containing flame retardant is used alone. Compared to the case where it is used, the different flame-retarding mechanisms make it difficult to ignite, shorten the after-flame time, and can also suppress drip, which can significantly improve the flame retardancy as artificial hair. .

  Examples of the phosphorus compound (C) comprising the organic cyclic phosphorus compound and / or the phosphoric ester amide compound used in the present invention include compounds having structures represented by the general formulas (5) to (13).

  Specific examples of the compound represented by the general formula (5) include the following formula:

And the like.

  Specific examples of the compound represented by the general formula (6) include the following formula:

And the like.

  Specific examples of the compound represented by the general formula (7) include the following formula:

And the like.

  Specific examples of the compound represented by the general formula (8) include the following formula:

And the like.

  In the compound represented by the general formula (9), r in the formula represents an integer of 1 to 5, and preferably 1 to 3. Specific examples of the compound represented by the general formula (9) include the following formula:

And the like.

  Specific examples of the compound represented by the general formula (10) include the following formula:

And the like.

  Specific examples of the compound represented by the general formula (11) include the following formula:

And the like.

  Specific examples of the compound represented by the general formula (12) include diphenyl (cyclohexylamide) phosphate, diphenyl (diethylamide) phosphate, diphenyl (morpholide) phosphate, diphenyl (octylamide) phosphate, diphenyl (benzylamide) phosphate, Examples thereof include diphenyl (allylamido) phosphate, diphenyl (anilide) phosphate, (dimorpholide) phenyl phosphate, and the like.

  Specific examples of the compound represented by the general formula (13) include the following formula:

And the like.

  In the present invention, the bromine-containing flame retardant (B) and the phosphorus compound (C) are used in an amount of 5 to 30 in total for the bromine-containing flame retardant (B) and the phosphorus compound (C) with respect to 100 parts by weight of the polyester (A). It is preferably part by weight, more preferably 6 to 27 parts by weight, and even more preferably 7 to 25 parts by weight. If the amount of the bromine-containing flame retardant (B) and phosphorus compound (C) used is less than 5 parts by weight, the flame retardancy effect tends to be difficult to obtain, and if it exceeds 30 parts by weight, the mechanical properties of the obtained artificial hair , Heat resistance and drip resistance tend to be impaired.

  In the present invention, the weight ratio of the bromine-containing flame retardant (B) and the phosphorus compound (C) is preferably 90/10 to 10/90, more preferably 80/20 to 20/80, and 70/30 to 30/70. Further preferred. When the weight ratio exceeds 90/10 or less than 10/90, the effect of the combined use of the bromine-containing flame retardant (B) and the phosphorus compound (C) is not expressed, and each is used alone There is a tendency that the flame retardant effect is reduced.

  In the present invention, by adding organic fine particles (D) and / or inorganic fine particles (E), fine protrusions are formed on the fiber surface, and natural luster close to human hair when used as artificial hair. Can be adjusted.

  The organic fine particle (D) may be an organic resin component having a structure that is incompatible or partially incompatible with the main component polyester (A), bromine-containing flame retardant (B) and phosphorus compound (C). For example, polyarylate, polyamide, fluororesin, silicon resin, cross-linked acrylic resin, cross-linked polystyrene and the like are preferably used. These may be used alone or in combination of two or more.

  As the inorganic fine particles (E), those having a refractive index close to the refractive indexes of the polyester (A), the bromine-containing flame retardant (B) and the phosphorus compound (C) are preferable because of the influence on the transparency and color developability of the fiber. Examples thereof include antimony trioxide compounds, antimony pentoxide compounds, sodium antimonate, calcium carbonate, 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. 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 amount of the organic fine particles (D) and / or inorganic fine particles (E) used in the present invention is not particularly limited, but is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyester (A). More preferably, it is 2-3 parts by weight, and still more preferably 0.3-2 parts by weight. When the amount of the organic fine particles (D) and / or inorganic fine particles (E) used exceeds 5 parts by weight, the appearance, hue and color developability of the resulting artificial hair tend to be impaired, and the amount is less than 0.1 parts by weight. Then, since fine protrusions formed on the fiber surface are reduced, the gloss adjustment on the fiber surface tends to be insufficient.

  The polyester-based composition used in the present invention comprises, for example, polyester (A), bromine-containing flame retardant (B) and phosphorus compound (C), and organic fine particles (D) and / or inorganic fine particles (E). After blending, it can be produced 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.

  For example, using a twin screw extruder with a screw diameter of 45 mm, the resin temperature is 260 to 300 ° C., melt kneading is performed at a discharge rate of 50 to 150 kg / hr and a screw rotation speed of 150 to 200 rpm, and the strand is taken out from the die. After cooling with water, the polyester composition of the present invention can be obtained by pelletizing with a strand cutter.

  The polyester-based artificial hair of the present invention can be produced by melt-spinning the polyester-based composition using 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 a 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 hot-drawn. The drawing is either a two-step method in which the spun yarn is once wound and then drawn, or a direct spin-drawing method in which the drawn yarn is continuously drawn without being wound up. It may be. The thermal 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 flame retardant polyester 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. It can be included. In addition, in the polyester-based artificial hair of the present invention, a primary fiber can be obtained by incorporating a pigment.

  The flame-retardant polyester artificial hair of the present invention thus obtained is a non-crimped raw fiber, and its fineness is usually 10 to 100 dtex, more preferably 20 to 90 dtex. Is suitable for artificial hair. When the fineness of the flame-retardant polyester artificial hair is less than 10 dtex, the fine hair tends to be too thin to maintain its performance as an artificial hair, and when it exceeds 100 dtex, it tends to be too thick and hard, resulting in a plastic-like feel. There is.

  The flame-retardant polyester-based artificial hair of the present invention has heat resistance capable of using a beauty heat appliance (hair iron) at 160 to 200 ° C., is difficult to ignite, and has self-extinguishing properties. Is preferred.

  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.

  In the present invention, pigments, dyes, auxiliaries and the like used for dyeing are preferably those having weather resistance and flame retardancy.

  The 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. Moreover, the flame-retardant polyester artificial hair of the present invention is appropriately matte due to the unevenness of the fiber surface, and can be used as artificial hair. The flame-retardant polyester artificial hair of the present invention can be made closer to human hair by using an oil agent such as a fiber surface treatment agent and a softening agent to give a touch and feel.

  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.

(Fineness)
Using 100 filaments having a length of 1 m as one tow, the weight of 10 tows was measured, and the average value was defined as the fineness.

(Strength and elongation)
A filament having a length of 40 mm was taken, 10 mm on both ends of the filament was sandwiched with a backing sheet (thin paper) to which a double-sided tape with an adhesive was applied, and air-dried overnight to prepare a sample having a length of 20 mm. A sample is mounted on a testing machine (INTESCO Model 201 (manufactured by Intesco)), and a tensile test is performed under conditions of 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. The strength and elongation were measured. The test was repeated 10 times under the same conditions, and the average value was defined as the filament elongation.

(Glossy)
A tow filament having a length of 30 cm and a total fineness of 100,000 dtex was 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

(transparency)
A tow filament having a length of 30 cm and a total fineness of 100,000 dtex was 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 compared to standard filament

(Feel)
A tow filament having a length of 30 cm and a total fineness of 100,000 dtex was touched by hand to evaluate the stickiness of the filament surface.
○: No sticky feeling △: Some sticky feeling ×: Sticky feeling

(Flame retardance)
a) Flammability A filament having a fineness of about 50 dtex was cut into a length of 150 mm, 0.7 g was bundled, and one end was clamped and fixed to a stand, and suspended vertically. An evaluation was made by indirectly burning a 20 mm flame for 3 seconds on a fixed filament having an effective length of 120 mm and burning it.
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

b) Limiting oxygen index (LOI)
A filament of 16 cm / 0.25 g was weighed, the ends were lightly collected with double-sided tape, and sandwiched and twisted with a suspender. When the twist was sufficiently applied, the center of the sample was folded in half and the two were twisted, and the ends were fixed with cello tape (registered trademark) so that the total length became 7 cm. Pre-drying was performed at 105 ° C. for 60 minutes, and further drying was performed for 30 minutes or more with a desiccator. The dried sample was adjusted to a predetermined oxygen concentration, and after 40 seconds, it was ignited from the top with an igniter throttled to 8 to 12 mm. The oxygen concentration that burned 5 cm or more or continued burning for 3 minutes or more was examined, and the test was repeated three times under the same conditions to obtain the critical oxygen index.

(Iron set property)
The iron set property is an index of the ease of curling with a hair iron and the retention of the curled shape.

  The filament was clamped between hair irons heated to 180 ° C. and preheated by handling 3 times. At this time, the fusion between the filaments and the shrinkage / thread breakage were visually evaluated.

  Next, the preheated filament was beaten on a hair iron, held for 10 seconds, and the iron was pulled out. The ease of pulling out (rod-out property) at this time and the curl retaining property (setting property) when pulled out were visually evaluated.

a) Fusion ○: No fusion is observed in the filament Δ: Slightly fused part is seen ×: Many fused parts are seen b) Crimp / Thread breakage ○: Filament No crimping or thread breakage is observed. Δ: Slightly crimped or thread broken parts are observed. X: Many crimped or thread broken parts are observed. C) Rod out property. ○: The iron is pulled out smoothly. △: Some resistance was felt when pulling out the iron ×: Difficult to pull out the iron d) Setability ○: The curl shape was kept well △: Some curl shape Breakage was observed ×: Curled shape was hardly retained

Examples 1-8
The composition having the ratio shown in Table 1 is dried to a water content of 100 ppm or less, and colored polyester pellets PESM6100 BLACK (manufactured by Dainichi Seika Kogyo Co., Ltd., carbon black content 30%, polyester is included in polyester (A)) Two parts were added and dry blended. Next, the blend was supplied to a twin-screw extruder, melt-kneaded at a cylinder temperature of 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 40 nozzle holes shown in FIG. 1 at a cylinder temperature of 280 ° C., air-cooled with cooling air at 20 ° C., and wound at a speed of 100 m / min. An undrawn yarn was obtained. The obtained unstretched yarn was stretched 4 times using a heat roll heated to 85 ° C., further heat-treated using a heat roll heated to 200 ° C., wound up at a speed of 30 m / min. A polyester fiber (multifilament) having a fiber fineness of around 65 dtex was obtained.

  Table 2 shows the results of evaluating the strength, gloss, transparency, tactile sensation, flame retardancy, and iron setability using the obtained polyester fibers.

Comparative Examples 1-3
The composition having the ratio shown in Table 1 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 2 shows the results of evaluating the strength, gloss, transparency, tactile sensation, flame retardancy, and iron setability using the obtained fibers.

* 1: Polyethylene terephthalate (Kanebo Gosei Co., Ltd.)
* 2: Bromine-containing phosphate ester (manufactured by Daihachi Chemical Industry Co., Ltd.)
* 3: Brominated epoxy flame retardant (Sakamoto Pharmaceutical Co., Ltd.)
* 4: Organocyclic phosphorus compound (manufactured by Sanko Co., Ltd.)
* 5: Phosphate ester amide (manufactured by Shikoku Chemicals Co., Ltd.)
* 6: Polyarylate (Unitika Ltd.)
* 7: Calcium phosphate (Maruo Calcium Co., Ltd.)
* 8: Phosphite antioxidant (Asahi Denka Kogyo Co., Ltd.)

  As shown in Table 2, compared to the comparative example, in the examples, the gloss, transparency, tactile sensation, iron set property, etc. are excellent, and a specific brominated flame retardant and a specific phosphorus flame retardant are used in combination. Thus, it was confirmed to have high flame retardancy. Therefore, the artificial hair using the specific brominated flame retardant of the present invention and the specific phosphorus-based flame retardant maintains gloss and transparency while maintaining the mechanical and thermal properties of the polyester compared to the conventional artificial hair. It has been confirmed that it can be effectively used as artificial hair with improved tactile feel and setability.

It is a nozzle hole sectional drawing of the spinneret in the melt spinning machine used in order to spin the flame-retardant polyester type artificial hair of the present invention.

Claims (12)

Polyester (A) comprising at least one of polyalkylene terephthalate and / or copolymerized polyester mainly composed of polyalkylene terephthalate, brominated epoxy flame retardant, brominated phenoxy resin flame retardant and brominated phosphate ester flame retardant A bromine-containing flame retardant comprising at least one of (B), and a phosphorus compound (C) comprising an organic cyclic phosphorus compound and / or a phosphoric ester amide compound,
A flame-retardant polyester-based artificial material comprising a composition obtained by melt-kneading 5 to 30 parts by weight of a mixture of the bromine-containing flame retardant (B) and the phosphorus compound (C) with respect to 100 parts by weight of the polyester (A) hair. The flame-retardant polyester artificial hair according to claim 1, wherein the weight ratio of the bromine-containing flame retardant (B) and the phosphorus compound (C) is 90/10 to 10/90. The flame-retardant polyester artificial hair according to claim 1 or 2, wherein the polyalkylene terephthalate is at least one selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate. The bromine-containing flame retardant (B) is at least one selected from the group consisting of brominated epoxy flame retardants and / or brominated phenoxy resin flame retardants represented by the general formulas (1) to (4). The flame-retardant polyester artificial hair according to claim 1, 2 or 3.

(In the formula, m represents an integer of 0 to 100.)

(In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms, n is 0 to 100, and x is an integer of 0 to 5.)

(In the formula, R ² is an alkyl group having 1 to 10 carbon atoms, p is 0 to 100, and y is an integer of 0 to 5.)

(In the formula, q represents any integer of 80 to 200.)   Bromine-containing flame retardant (B) is tris (bromoethyl) phosphate, tris (bromopropyl) phosphate, tris (dibromopropyl) phosphate, tris (bromobutyl) phosphate, tris (dibromobutyl) phosphate, tris (bromoneopentyl) phosphate, tris The flame-retardant polyester artificial hair according to claim 1, 2 or 3, which is at least one brominated phosphate compound selected from the group consisting of (dibromoneopentyl) phosphate and tris (tribromoneopentyl) phosphate. . The phosphorus compound (C) is represented by the general formulas (5) to (13):

(Wherein R ¹ is a hydrogen atom or a linear or branched alkyl group, which may be the same or different, and R ² is a hydrogen atom, a linear or branched alkyl group, And represents a chain or branched hydroxyalkyl group, cycloalkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted aralkyl group.)

(Wherein R ¹ is a hydrogen atom or a linear or branched alkyl group, which may be the same or different, and R ³ is a divalent linear or branched alkylene group, Chain or branched hydroxyalkyl group, cycloalkylene group, alkylene group having ether oxygen in the main chain, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, α, α′-xylylene group, substituted- An α, α′-xylylene group, an α, α′-metaxylylene group, or a substituted-α, α′-xylylene group is shown.)

(In the formula, R ¹ is a hydrogen atom or a linear or branched alkyl group, which may be the same or different, and R ⁴ is a hydrogen atom, a linear or branched alkyl group, Represents an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group.)

Wherein R ¹ is a hydrogen atom or a linear or branched alkyl group, which may be the same or different, and R ⁵ is a divalent linear or branched alkylene group, cyclo Alkylene group, alkylene group having ether oxygen in the main chain, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, α, α′-xylylene group, substituted-α, α′-xylylene group, α, An α′-metaxylylene group or a substituted-α, α′-xylylene group is shown.)

(Wherein R ¹ is a hydrogen atom or a linear or branched alkyl group, which may be the same or different, and R ⁶ is a divalent linear or branched alkylene group, or A cycloalkylene group, R ⁷ is a hydrogen atom, or a linear or branched alkyl group, and r is any one of 1 to 5)

(In the formula, R ¹ is a hydrogen atom or a linear or branched alkyl group, which may be the same or different, and R ⁸ and R ⁹ are a hydrogen atom, a linear or branched alkyl group, respectively. A cycloalkyl group, which may be the same or different, and Y is a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or (It is an unsubstituted aralkyl group, and s represents 1 or 2.)

(Wherein R ¹ is a hydrogen atom or a linear or branched alkyl group, which may be the same or different, and R ¹⁰ is a divalent linear or branched alkylene group, A hydroxyalkyl group having a chain or a branch, a cycloalkylene group, an alkylene group having an ether oxygen in the main chain, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and X is an oxygen atom or a sulfur atom And t represents 0 or 1.)

(In the formula, R ¹¹ is a hydrogen atom or a linear or branched alkyl group, which may be the same or different, and R ¹² and R ¹³ are a hydrogen atom, a linear or branched alkyl group, respectively. A straight-chain or branched hydroxyalkyl group, a cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, each of which may be the same or different, and u is 1 Or 2 is shown.)

(In the formula, R ¹¹ is a hydrogen atom or a linear or branched alkyl group which may be the same or different, and R ¹⁴ and R ¹⁵ are divalent linear or branched alkylene. Group, a linear or branched hydroxyalkyl group, a cycloalkylene group, an alkylene group having ether oxygen in the main chain, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. Or different.)
The flame-retardant polyester artificial hair according to claim 1, 2 or 3, which is an organic cyclic phosphorus compound and / or a phosphoric ester amide compound represented by the formula: The flame-retardant polyester artificial hair according to claim 1, 2, 3, 4, 5 or 6, further comprising organic fine particles (D) and / or inorganic fine particles (E). The flame-retardant polyester artificial hair according to claim 7, wherein the organic fine particles (D) comprise 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 selected from the group consisting of an antimony trioxide compound, an antimony pentoxide compound, sodium antimonate, calcium carbonate, silicon oxide, titanium oxide, aluminum oxide, zinc oxide, talc, kaolin, montmorillonite, bentonite, and mica. The flame-retardant polyester artificial hair according to claim 7, comprising at least one selected. The flame-retardant polyester artificial hair according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9, which is non-crimped raw silk. The flame-retardant polyester-based artificial hair according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, wherein the artificial-hair-dyed hair is attached. The flame-retardant polyester-based artificial hair according to claim 1, wherein the single fiber fineness is 10 to 100 dtex.

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