KR20070001150A - Flame Retardant Polyester Hair - Google Patents

Abstract

Provides a flame retardant polyester artificial hair excellent in spinning processability, maintaining fiber properties such as heat resistance and elongation, and excellent in curl retention and iron setting properties. Excellent spinning processability by melt spinning a polyester obtained by melt kneading a phosphorus-containing flame retardant and / or a bromine-containing flame retardant with at least one compound selected from the group consisting of carbodiimide compounds, bisoxazolin compounds, and isocyanate compounds Fiber properties such as heat resistance and elongation are maintained, and flame retardant polyester artificial hair having excellent curl holding power and iron setting properties is obtained.

Flame retardant polyester artificial hair, phosphorus containing flame retardant, bromine containing flame retardant, carbodiimide compound

Description

Flame retardant polyester artificial hair {FLAME-RETARDANT POLYESTER ARTIFICIAL HAIR}

The present invention is formed of a composition obtained by melt kneading a polyester with a phosphorus-containing flame retardant and / or bromine-containing flame retardant and at least one compound selected from the group consisting of carbodiimide compounds, bisoxazolin compounds, and isocyanate compounds. It relates to a flame retardant polyester fiber for artificial hair. More specifically, the present invention relates to a flame-retardant polyester artificial hair having excellent spin processability, maintaining fiber properties such as heat resistance and elongation, and having excellent curl retention and iron setting properties.

Fibers composed of polyethylene terephthalate or polyester mainly composed of polyethylene terephthalate have high melting point, high elastic modulus, excellent heat resistance and chemical resistance, so that curtains, rugs, medical treatments, blankets, sheets, and table cloths (table It is widely used in cloth, furniture cover, closet, artificial hair, automotive interior materials, outdoor reinforcement, safety net, and the like.

On the other hand, in hair products such as wigs, hair wigs, hair extensions, hair bands, and doll hairs, human hair and artificial hair (modacryl fiber, polyvinyl chloride fiber) and the like have conventionally been used. However, the provision of human hair has become difficult, and the importance of artificial hair has increased. As an artificial hair material, modacryl has been used a lot in view of flame retardancy, but it is insufficient in terms of heat resistance temperature. In recent years, artificial hair fibers using a fiber composed mainly of polyesters represented by polyethylene terephthalate having excellent heat resistance have been proposed. However, in using it 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, from polyesters copolymerized with flame retardant monomers containing phosphorus atoms. The method of making a fiber, the method of making a flame retardant into a polyester fiber, etc. are known.

As a method of copolymerizing the former flame retardant monomer, for example, a method of copolymerizing a phosphorus compound having a phosphorus atom as a reducer and having good thermal stability (Patent Document 1) and a method of copolymerizing carboxy phosphinic acid (Patent Document 2) And the method of mix | blending or copolymerizing a phosphorus compound with polyester containing polyarylate (patent document 3), etc. are proposed. As the above flame-retardant technique applied to artificial hair, for example, a polyester fiber obtained by copolymerizing a phosphorus compound has been proposed (Patent Document 4). However, since artificial hair is required to have high flame resistance, in order to use these co-polyester fibers as artificial hair, the amount of copolymerization must be increased. As a result, the heat resistance of the polyester is greatly reduced, resulting in melt spinning. If it becomes difficult or the flame approaches, ignition and combustion are not performed, but another problem of melting and driping occurs.

On the other hand, as a method of containing the latter flame retardant, a method of containing a halogenated cycloalkane compound of fine particles in a polyester fiber (patent document 5), a method of containing a bromine atom-containing alkyl cyclohexane (patent document 6), and the like It is proposed. In the method of containing a flame retardant in the polyester fiber, in order to obtain sufficient flame resistance, it is necessary to make the containing treatment temperature at a high temperature of 150 ° C. or higher, or to carry out the containing treatment time for a long time, or to use a large amount of flame retardant. There is a problem that must be done, and problems such as a decrease in fiber properties, a decrease in productivity, and an increase in manufacturing cost occur.

On the other hand, in recent years, it is necessary to recover and reuse polyester products discarded at the point of resource reuse and environmental protection. In particular, foodstuff using polyethylene terephthalate, which has a high amount of polyester and is expected to increase in the future. Bottles for liquids are products that are worth reclaiming and reuse, and the attempt has actually begun. When the recovered polyester is chopped and made into fibers, the stretching step is performed such that the breaking elongation usually performed at the time of weaving medical fibers is 30% by impurities such as additives and foreign substances contained in the polyester. In this case, since the thread trimming occurs frequently, the operability is remarkably lowered, it is difficult to produce a general purpose medical multifilament from the recovered polyester. In order to maintain fiber performance and to enable industrial production, it is essential to contain 5% by weight or less of impurities other than polyester in polyester fibers, and it is necessary to use a polyester bottle recovered as a raw material. There is. However, a bottle for an edible liquid requires some heat resistance in the bottle opening portion in order to seal the heat sterilized liquid. For this reason, it is difficult to remove these other raw materials, as many as the raw material of a polyester bottle uses a different raw material, and makes a polyester bottle a raw material.

As described above, artificial hairs having excellent heat resistance, elongation, and other physical properties of the conventional polyester fiber and having excellent setting properties and flame retardancy, or artificial hairs having excellent setting properties and flame retardancy formed using recovered polyester have not yet been obtained. It is not.

Patent Document 1: Japanese Patent Application Publication No. 55-41610

Patent Document 2: Japanese Patent Application Publication No. 53-13479

Patent Document 3: Japanese Patent Application Laid-Open No. 11-124732

Patent Document 4: Japanese Patent Application Laid-Open No. 3-27105

Patent Document 5: Japanese Patent Application Laid-Open No. 3-57990

Patent Document 6: Japanese Patent Application Laid-Open No. 1-24913

[Initiation of invention]

[Problem to Solve Invention]

The present invention is to solve the conventional problems as described above, to provide a flame-retardant polyester artificial hair excellent in spinning workability, maintaining fiber properties such as heat resistance, elongation, excellent curl holding power, iron setting properties. The purpose.

[Means for solving the problem]

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors have at least selected from the group which consists of a phosphorus containing flame retardant and / or bromine containing flame retardant in a polyester, a carbodiimide compound, a bisoxazoline compound, and an isocyanate compound. By melt spinning a composition obtained by melt kneading one compound, it is possible to obtain a flame-retardant polyester artificial hair excellent in spinning workability, maintaining fiber properties such as heat resistance and elongation, and excellent in curl retention and iron setting properties. It was found that the present invention was completed.

That is, this invention is a phosphorus containing flame retardant and / or bromine containing flame retardant with respect to 100 weight part of polyester (A) which consists of 1 or more types of copolymerized polyester mainly having polyalkylene terephthalate and polyalkylene terephthalate. (B) 0.05-30 weight part of at least 1 sort (s) of compound (C) chosen from the group which consists of 5-30 weight part, a carbodiimide compound, a bisoxazoline compound, and an isocyanate compound, and is obtained by melt-kneading, Intrinsic viscosity is 0.5- It relates to a flame-retardant polyester artificial hair formed of a composition of 1.4.

In addition, the flame-retardant polyester artificial hair is preferably non-critical green yarn, woven, and short fiber fineness of 10 to 100 dtex.

According to the present invention, it is possible to obtain a flame-retardant polyester artificial hair excellent in spinning workability, maintaining fiber properties such as heat resistance and elongation, and excellent in curl holding power and iron setting properties.

The flame-retardant polyester artificial hair of the present invention contains polyester (A), phosphorus-containing flame retardant, and / or bromine composed of one or more kinds of copolyesters mainly composed of polyalkylene terephthalate and polyalkylene terephthalate. Fiber obtained by melt kneading at least one compound (C) selected from the group consisting of a flame retardant (B), a carbodiimide compound, a bisoxazoline compound and an isocyanate compound, and melt spinning the composition having an intrinsic viscosity of 0.5 to 1.4 to be.

As co-polyester mainly consisting of polyalkylene terephthalate or polyalkylene terephthalate contained in the polyester (A) used for this invention, polyethylene terephthalate, polypropylene terephthalate, polybutylene tere, for example. And polyalkylene terephthalates such as phthalates and / or copolymerized polyesters containing a small amount of copolymerization components mainly as polyalkylene terephthalates. In addition, the used PET bottle can be made into a flake shape and reused.

The said main body means containing 80 mol% or more.

As said copolymerization component, for example, isophthalic acid, ortho phthalic acid, naphthalene dicarboxylic acid, paraphenylene dicarboxylic acid, trimellitic acid, pyromellitic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid Polycarboxylic acids such as sebacic acid and dodecane diacid, derivatives thereof, dicarboxylic acids containing sulfonic acid salts such as 5-sodium sulfo isophthalic acid and 5-sodium sulfo isophthalic acid dihydroxy ethyl, derivatives thereof, 1, 2-propane diol, 1,3-propane diol, 1,4-butane diol, 1,6-hexane diol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, polyethylene glycol, trimethylolpropane, Pentaerythritol, 4-hydroxy benzoic acid, (epsilon) -caprolactone, etc. are mentioned.

The copolymerized polyester is usually produced by containing a small amount of a copolymerization component in a polymer of terephthalic acid and / or its derivative (for example, methyl terephthalate) and an alkylene glycol, which is mainly used, for its stability and operation. Although it is preferable from the point of simplicity, you may manufacture by polymerizing what contained the monomer or oligomer component which are a small copolymerization component in the mixture of the main terephthalic acid and / or its derivative (for example, methyl terephthalate), and alkylene glycol. .

The said copolymer polyester should just polycondense the said copolymerization component to the main chain and / or side chain of the polyalkylene terephthalate which becomes a main body, and there is no special limitation etc. in the method of copolymerization.

As a specific example of the copolyester mainly having the said polyalkylene terephthalate, For example, the polyester which mainly copolymerized the polyethylene terephthalate and copolymerized the ethylene glycol ether of bisphenol A, 1, 4- cyclohexane dimethanol The polyester which copolymerized the copolymer, the polyester which copolymerized 5-hydroxysulfo isophthalic-acid dihydroxy ethyl, etc. are mentioned.

The said polyalkylene terephthalate and copolyester may be used by 1 type, and may be used in combination of 2 or more type. Among these, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, copolymerized polyester (polyester terephthalate mainly, copolymerized with ethylene glycol ether of bisphenol A, 1,4-cyclohexanedimethanol Polyester copolymerized with polypropylene, polyester copolymerized with 5-sodium sulfo isophthalic acid dihydroxy ethyl, and the like) are preferable, and these are also preferably mixed two or more kinds.

There is no restriction | limiting in particular in the phosphorus containing flame retardant used for the phosphorus containing flame retardant and / or bromine containing flame retardant (B) in this invention, It can be used if it is a phosphorus containing flame retardant generally used.

As a phosphorus containing flame retardant used as a phosphorus containing flame retardant and / or a bromine containing flame retardant (B) in this invention, a phosphate type compound, a phosphonate type compound, a phosphinate type compound, a phosphine oxide type compound, for example And phosphonite-based compounds, phosphinite-based compounds, phosphine-based compounds, and condensed phosphate ester compounds represented by the general formula (1).

(Wherein, R ¹ is a monovalent aromatic hydrocarbon group or an aliphatic hydrocarbon group, they may be the same or different, respectively, R ² is a divalent aromatic hydrocarbon group, when two or more are included, they may be the same or different, n The condensed phosphate ester compound represented by 0) may be mentioned. These may be used by 1 type and may be used in combination of 2 or more type.

Specific examples of the phosphorus-containing flame retardant include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethyl hexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate and tris (Isopropyl phenyl) phosphate, tris (phenylphenyl) phosphate, trinephthyl phosphate, cresylphenyl phosphate, xyleneyl diphenyl phosphate, triphenyl phosphine oxide, tricresyl phosphine oxide, methanephosphonic acid diphenyl, and Resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate, as well as diethyl phenylphosphonic acid, etc. Etc., expression:

And condensed phosphate ester compounds represented by the above.

In these, the condensed phosphate ester type compound represented by General formula (1) is preferable.

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

Specific examples of the bromine-containing flame retardant used as the phosphorus-containing flame retardant and / or the bromine-containing flame retardant (B) in the present invention include pentabromotoluene, hexabromobenzene, decabromodiphenyl, decabromodiphenyl ether, Bis (tribromophenoxy) ethane, tetrabromo phthalic anhydride, ethylene bis (tetrabromophthalimide), ethylene bis (pentabromophenyl), octabromotrimethylphenylindan, tris (tribromoneopentyl) Bromine-containing phosphate esters such as phosphate, brominated polystyrene, brominated polybenzyl acrylates, brominated epoxy oligomers, brominated phenoxy resins, brominated polycarbonate oligomers, tetrabromobisphenol A, tetrabromobisphenol A-bis ( 2,3-dibromopropyl ether), tetrabromobisphenol A-bis (allyl ether), tetrabromobisphenol A-bis (hydroxyethyl ether) Bromine-containing isocyanuric compounds such as bromine-containing triazine compounds such as tetrabromobisphenol A derivatives and tris (tribromophenoxy) triazine and tris (2,3-dibromopropyl) isocyanurate Etc. can be mentioned. These may be used by 1 type and may be used in combination of 2 or more type.

Among these, bromine-containing phosphate ester flame retardants, brominated polystyrene flame retardants, brominated benzyl acrylate flame retardants, brominated polycarbonate flame retardants, tetrabromobisphenol A derivatives, bromine-containing triazine compounds, and bromine-containing isocyanuric acid compounds desirable.

As for the usage-amount of the phosphorus containing flame retardant and / or bromine containing flame retardant (B) in this invention, 5-30 weight part is preferable with respect to 100 weight part of polyester (A), 6-25 weight part is more preferable, 7 20 weight part is more preferable. When the amount of the phosphorus-containing flame retardant and / or the bromine-containing flame retardant (B) is less than 5 parts by weight, it is difficult to obtain a flame retardant effect, and when it is more than 30 parts by weight, mechanical properties, heat resistance and drip resistance tend to be impaired. .

The carbodiimide compound of (C) component used for this invention is a compound which has a carbodiimide group represented by at least 2 (-N = C = N-) in a molecule | numerator, There is no limitation in particular, For example, Phenyl carbodiimide, di-cyclohexyl carbodiimide, di-2,6-dimethylphenyl carbodiimide, diisopropylcarbodiimide, dioctyldecyl carbodiimide, di-o-tolyl carbodiimide, N-tolyl -N'-phenyl carbodiimide, N-tolyl-N'-cyclohexyl carbodiimide, di-p-tolyl carbodiimide, di-p-nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide , Di-p-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di-2,5- Dichlorophenylcarbodiimide, p-phenylene-bis-o-tolylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene-bis-dicyclo Silk carbodiimide, p-phenylene-bis-di-p-chlorophenylcarbodiimide, hexamethylene-bis-dicyclohexyl carbodiimide, ethylene-bis-diphenyl carbodiimide, ethylene-bis-di-cyclo Mono or dicarbodiimide compounds such as hexyl carbodiimide, poly (1,6-hexamethylenecarbodiimide), poly (4,4'-methylenebiscyclohexylcarbodiimide), poly (1,3-cyclo Hexylene carbodiimide), polycarbodiimide such as poly (1,4-cyclohexylenecarbodiimide), poly (4,4'-diphenylmethanecarbodiimide), poly (3,3'-dimethyl -4,4'-diphenylmethanecarbodiimide), poly (naphthylene carbodiimide), poly (p-phenylene carbodiimide), poly (m-phenylene carbodiimide), poly (tolyl carbodiimide Mead), poly (diisopropylphenylene carbodiimide), poly (methyl-diisopropylphenylene carbodiimide), poly (triethylphenylene carbodiimide), poly (triisope Aromatic polycarbodiimides, such as lobil phenylene carbodiimide), etc. are mentioned, As a commercial item, Starbox sol I and Baybacsol P (all registered trademark) of Bayer AG are mentioned. The carbodiimide compound may be used alone or in combination of two or more thereof.

The bisoxazolin compound of (C) component used for this invention does not have limitation in particular, For example, 2,2'-methylene bis (2-oxazoline) and 2,2'-ethylene bis (2-oxa) Sleepy), 2,2'-ethylene bis (4-methyl-2-oxazoline), 2,2'-propylene bis (2-oxazoline), 2,2'-tetramethylene bis (2-oxazoline), 2,2'-hexamethylenebis (2-oxazoline), 2,2'-octamethylene bis (2-oxazoline), 2,2'-p-phenylene bis (2-oxazoline), 2,2 '-p-phenylene bis (4-methyl-2-oxazoline), 2,2'-p-phenylene bis (4,4-dimethyl-2-oxazoline), 2,2'-p-phenylene Bis (4-phenyl-2-oxazoline), 2,2'-m-phenylene bis (2-oxazoline), 2,2'-m-phenylene bis (4-methyl-2-oxazoline), 2,2'-m-phenylene bis (4,4-dimethyl-2-oxazoline), 2,2'-m-phenylene bis (4-phenyl-2-oxazoline), 2,2'-o -Phenylene bis (2-oxazoline), 2,2'-phenyl bis (4-methyl-2-oxazoline), 2,2'-bis (2-oxazoline), 2,2'-bis (4 -Methyl-2-oxazoline), 2,2'-bis (4-methyl-2-oxazole ), 2,2'-bis (4-phenyl-2-oxazoline) and the like. Such a bisoxazoline compound may be used independently or may be used together 2 or more types.

Examples of the isocyanate of the component (C) used in the present invention include aliphatic or aromatic various diisocyanates. The aliphatic diisocyanate may not only be a linear structure, but may contain a branched structure or an alicyclic structure, or may contain an oxygen atom. The aromatic diisocyanate is not particularly limited as long as it contains a divalent aromatic hydrocarbon group in the molecule. As aliphatic diisocyanate, it is 1, 3- trimethylene diisocyanate, 1, 4- tetramethylene diisocyanate, 1, 6- hexamethylene diisocyanate, 1, 9- nonamethylene diisocyanate, 1, 10-, for example. Decamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, hexamethylene diisocyanate-buretena, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isoprondi Isocyanate, 1, 4- cyclohexane diisocyanate, 4,4'- dicyclohexyl methane diisocyanate, hydrogenated xylene diisocyanate, 2,2'- diethyl ether diisocyanate, etc. are mentioned. Moreover, as aromatic diisocyanate, p-phenylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, 4,4'- diphenyl diisocyanate, 1, 5- naphthalene diisocyanate, 4,4'- diphenyl, for example Methane diisocyanate, 3,3'-methyleneditolylene-4,4'-diisocyanate, tolylene diisocyanate-trimethylolpropane adduct, triphenylmethane triisocyanate, 4,4'-diphenylether diisocyanate, tetrachloro Phenylene diisocyanate, 3,3'- dichloro-4,4'- diphenylmethane diisocyanate, a triisocyanate phenylthio phosphate, etc. are mentioned. Such isocyanate compounds may be used independently or may be used together 2 or more types.

The usage-amount of the at least 1 sort (s) of compound (C) chosen from the group which consists of a carbodiimide compound, a bisoxazoline compound, and an isocyanate compound in this invention is 0.05-10 weight part with respect to 100 weight part of polyester (A). Parts, preferably 0.1 to 8 parts by weight, more preferably 0.2 to 6 parts by weight. When the amount of the at least one compound (C) selected from the group consisting of a carbodiimide compound, a bisoxazoline compound and an isocyanate compound is less than 0.05 part by weight, there is a tendency that the effect is small against the fluidity decrease or the bleeding inhibition. When the amount exceeds 10 parts by weight, the flame retardancy and the mechanical strength of the flame retardant polyester artificial hair tend to be lowered.

The composition obtained by melt-kneading the components (A), (B) and (C) of the present invention can obtain good spinning processability by adjusting the amount of the component (C) used and setting the intrinsic viscosity to 0.5 to 1.4. As intrinsic viscosity of a composition, 0.5-1.4 are preferable and it is more preferable that it is 0.6-1.2. When the intrinsic viscosity of the composition is less than 0.5, a tendency of lowering the mechanical strength of the resulting fiber occurs, and when it exceeds 1.4, the melt viscosity increases with increasing molecular weight, making melt spinning difficult, or unevenness tending to be uneven. Occurs.

The polyester composition used for this invention can be manufactured by melt-kneading, for example using various general kneading machines, after carrying out dry blending of (A), (B) and (C) component.

As an example of the said mixer, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, a kneader, etc. are mentioned, for example. Among these, a twin screw extruder is preferable at the point of adjustment of kneading degree, and the simplicity of operation.

For example, using a twin screw extruder having a screw diameter of 45 mm, the barrel temperature is set to 260 to 300 ° C, melt kneaded at a discharge amount of 50 to 150 kg / hr, and a screw rotation speed of 150 to 200 rpm, and the strand ( After taking the strand) and water-cooling, it is pelletized using a strand cutter, and the composition of this invention can be obtained.

The polyester artificial hair of the present invention can be produced by melt spinning the polyester composition by a conventional melt spinning method.

That is, melt spinning is carried out at, for example, the temperature of an extruder, a gear pump, a detention, etc. at 270 to 310 ° C, the discharge yarn is passed through a heating tube, and then cooled to a glass transition point or less, and then to 50 to 5000 m / min. By taking off at a speed, an emission thread can be obtained. It is also possible to cool the discharge thread in a water tank containing cooling water and to perform fineness control. The temperature and length of the heating tube, the temperature and the amount of blowing air, the temperature of the cooling bath, the cooling time, and the take-up speed can be adjusted accordingly according to the discharge amount and the number of holes in the cage.

Although the obtained yarn is thermally stretched, the stretching may be performed by any of the two-step method of winding up and then stretching the yarn, and the method of direct spinning and stretching continuously without winding. The thermal stretching is performed by a single stage stretching method or a multistage stretching method of two or more stages. As a heating means in thermal drawing, a heating roller, a heat plate, a steam jet apparatus, a hot water tank, etc. can be used, These can also be used together suitably.

If necessary, the polyester artificial hair of the present invention may contain various additives such as a heat resistant agent, a light stabilizer, a fluorescent agent, an antioxidant, an antistatic agent, a pigment, a plasticizer, a lubricant, and the like. By containing a pigment, a primary fiber can be obtained.

The polyester-based artificial hair of the present invention thus obtained is a non-critical raw silk fiber, and its fineness is usually 10 to 100 dtex, preferably 20 to 90 dtex. Moreover, as artificial hair, it is preferable to have heat resistance which can use a beauty hot air balloon (hair iron) at 160-200 degreeC, it is hard to ignite and it has self-extinguishing property.

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

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

The polyester artificial hair of this invention is excellent in the curl setting property using a beauty hot air balloon (hair iron), and is excellent also in curl retention property. In addition, due to the irregularities of the surface of the fiber, the degree of glossiness is eliminated to an appropriate degree, and can be used for artificial hair. In addition, by using an oil agent such as a fiber surface treatment agent, a softening agent, it is possible to provide a touch and texture, and closer to human hair.

Moreover, the flame-retardant polyester artificial hair of this invention may be used together with other artificial hair materials, such as modacryl fiber, polyvinyl chloride fiber, and nylon fiber, and may be used together with human hair.

Best Mode for Carrying Out the Invention

Next, although an Example demonstrates this invention further more concretely based on an Example, this invention is not limited to these.

The measuring method of a characteristic value in this invention is as follows.

(Intrinsic Viscosity of Polyester)

Relative viscosity at 25 ° C. was measured using a Ubbellohde viscometer for a solution having a concentration of 0.5 g / dl using the same weight mixture of phenol and tetrachloroethane as a solvent. Calculated.

(Wherein η is the viscosity of the solution, η ₀ is the viscosity of the solvent, η _rel is the relative viscosity, η _sp is the specific viscosity, [η] is the intrinsic viscosity, and C is the concentration of the solution).

(Strength and elongation)

Tensile strength of the filament was measured using an INTESCO Model 201 manufactured by Intesco. A filament of 40 mm in length was taken, and 10 mm of both ends of the filament were inserted into a board (thin paper) to which a double-sided tape with adhesive was applied, and air-dried overnight to prepare a sample having a length of 20 mm. . A sample was mounted on the tester, the test was performed at a temperature of 24 ° C., a humidity of 80% or less, a load of 1/30 gF x fineness (denier), and a tensile speed of 20 mm / minute, and the elongation was measured. The test was repeated 10 times under the same conditions, and the average value was taken as the elongation of the filament.

(Heat resistance)

As an index of heat resistance evaluation, the heat shrinkage rate of the filament was measured using SSC5200H thermal analysis TMA / SS150C manufactured by Seiko Instruments Co., Ltd. (Seiko Instruments Inc.). Ten filaments having a length of 10 mm were taken, and a load of 5.55 mg / dtex was applied, and the heat shrinkage was measured in a range of 30 to 280 ° C at a temperature increase rate of 3 ° C / min.

(Flame retardant)

Cut the filament of fineness about 50dtex into length of 150mm, tie 0.7g, fasten one end by clamping it to the stand, and hang it vertically. 20 mm of sparks were contacted with a fixed filament having an effective length of 120 mm for 3 seconds, and burned to evaluate.

-combustibility-

◎: Afterflaming time is 0 seconds (not ignited)

○: afterglow time is less than 3 seconds

△: afterflaming time is 3 to 10 seconds

X: afterglow time is 10 second or more

Drip resistance

◎: Number of drips is 0

○: 5 or less drips

△: drip number 6 to 10 seconds

×: 11 or more drips

(Curl setting)

Wind the filament in the form of a filament into a pipe of 32 mmφ, curl set at 120 ° C. and a relative humidity of 100% for 60 minutes, and after aging at room temperature for 60 minutes, fix one end of the curled filament. Hanging, the condition of the curl was visually evaluated. Using this as an index of ease of applying curls, it is preferable that the length is short and curls are provided in good shape.

○: Good curling

△: curl slightly stretched

×: curl is stretched and the shape collapses

(Iron setting)

It is an index of the ease of curl setting by hair iron and the retention of curl shape. The filament was lightly sandwiched into a hair iron heated to 180 ° C., and skimmed three times to preheat. At this time, fusion between the filaments, combability, shrinkage of the filaments, and trimming are visually evaluated. The preheated filament is then wound around a hair iron, held for 10 seconds, and the iron is removed. The ease of pulling out at this time (load out property) and the retention of curl at the time of pulling out were visually evaluated.

(Examples 1 to 8)

The composition of the ratio shown in Table 1 is dried to 100 ppm or less of moisture content, and is made by polyester pellet PESM 6100 BLACK (made by Daiichi Seika Color & Chemicals Mfg. Co., Ltd.) for coloring, carbon black content 30 %, Polyester was added to 2 parts of (A) component, and it was dry-blended, it supplied to the twin screw extruder, melt-kneaded at 280 degreeC, and after pelletizing, it dried to 100 ppm or less of moisture content. Subsequently, a molten spinning machine was used to discharge molten polymer from a spinneret having 40 holes of a round nozzle having a nozzle diameter of 0.5 mmφ at 280 ° C, air-cooled by a cooling air at 20 ° C, wound at a speed of 100 m / min, and unstretched yarn. Got. The obtained non-drawn yarn was stretched four times using a heat roll heated at 85 ° C., heat treated using a heat roll heated at 200 ° C., wound at a rate of 30 m / min, and short fiber fineness was 50 dtex. Polyester fiber (multifilament) before and after was obtained.

* 1: polyethylene terephthalate, IV 0.60, manufactured by Kanebo Gohsen, Ltd.

* 2: The recovered PET bottle was washed and then crushed into flake shape, IV 0.65

* 3: Condensation phosphate ester, Daihachi Chemical Industry Co., Ltd. make

* 4: Brominated epoxy flame retardant, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.

* 5: aromatic poly carbodiimide, manufactured by Beyer

Table 2 shows the results of evaluating elongation, heat shrinkage, flame retardancy, curl holding force, and iron setting using the obtained fiber.

(Comparative Examples 1 and 2)

The composition of the ratio shown in Table 1 was dried to 100 ppm or less of moisture content, and it carried out similarly to the Example, and obtained polyester fiber (multifilament) of about 50 dtex of short fiber fineness.

Table 3 shows the results of evaluation of elongation, heat shrinkage, flame retardancy, curl holding force, and iron setting using the obtained fiber.

As shown in Table 2 and Table 3, in the examples, in the examples, the heat resistance, curl holding power, iron setting properties, etc. are excellent, and by using a carbodiimide compound, a bis oxazoline compound, an isocyanate compound It was confirmed that the intrinsic viscosity could be adjusted and had excellent spinning processability. Therefore, the artificial hair using this carbodiimide compound, bisoxazoline compound, and isocyanate compound improves heat resistance, iron setting property, etc., maintaining the mechanical and thermal properties of polyester compared with the conventional artificial hair. It was confirmed that it can be used effectively with the artificial hair.

According to the present invention, it is possible to provide a flame retardant polyester artificial hair having excellent spin workability and excellent curl retention and iron setting properties while maintaining fiber properties such as heat resistance and elongation.

Claims (11)

Phosphorus-containing flame retardant and / or bromine-containing flame retardant (B) 5 to 30 with respect to 100 parts by weight of polyester (A) composed of at least one kind of copolymerized polyester mainly composed of polyalkylene terephthalate and polyalkylene terephthalate. It is obtained by melt-kneading the weight part and 0.05-10 weight part of at least 1 sort (s) of the compound (C) chosen from the group which consists of a carbodiimide compound, a bisoxazoline compound, and an isocyanate compound, and formed with the composition which has an intrinsic viscosity of 0.5-1.4 , Flame retardant polyester artificial hair. The method of claim 1, A flame retardant polyester artificial hair wherein the polyalkylene terephthalate is at least one polymer selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate. The method of claim 1, Flame-retardant polyester artificial hair in which polyester (A) is a polyethylene terephthalate used for recycling from used PET bottles. The method according to any one of claims 1, 2 or 3, Phosphorus-containing flame retardants and / or bromine-containing flame retardants (B) include phosphate compounds, phosphonate compounds, phosphinate compounds, phosphine oxide compounds, phosphonite compounds, phosphinite compounds, and phosphine compounds Flame retardant polyester artificial hair, which is at least one compound selected from the group consisting of a compound and a condensed phosphate ester compound. The method according to any one of claims 1, 2 or 3, Phosphorus-containing flame retardants and / or bromine-containing flame retardants (B) include bromine-containing phosphate ester flame retardants, brominated polystyrene flame retardants, brominated benzyl acrylate flame retardants, brominated epoxy flame retardants, brominated phenoxy resin flame retardants, brominated polycarbonate flame retardants, A flame retardant polyester artificial hair, which is at least one compound selected from the group consisting of tetrabromobisphenol A derivatives, bromine-containing triazine compounds and bromine-containing isocyanuric acid compounds. The method according to any one of claims 1, 4 or 5, At least one compound (C) selected from the group consisting of a carbodiimide compound, a bisoxazoline compound and an isocyanate compound is p-phenylene-bis-o-tolylcarbodiimide, p-phenylene-bis-p- Chlorophenylcarbodiimide, ethylene-bis-diphenyl carbodiimide, poly (4,4'-methylenebiscyclohexylcarbodiimide), poly (4,4'-diphenylmethanecarbodiimide), poly (3 , 3'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylene carbodiimide), poly (Tolylcarbodiimide), poly (diisopropylphenylenecarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly (triethylphenylenecarbodiimide) and poly (triisopropylphenylenecarbodiimide The flame retardant polyester artificial hair which is at least 1 sort (s) chosen from the group which consists of mead). The method according to any one of claims 1, 4 or 5, At least one compound (C) selected from the group consisting of a carbodiimide compound, a bisoxazoline compound and an isocyanate compound is 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl -2-oxazoline), 2,2'-bis (4,4-dimethyl-2-oxazoline), 2,2'-bis (4-phenyl-2-oxazoline), 2,2'-bis ( 4-cyclohexyl-2-oxazoline), 2,2'-bis (4-benzyl-2-oxazoline), 2,2'-p-phenylene bis (2-oxazoline), 2,2'- m-phenylene bis (2-oxazoline), 2,2'-o-phenylene bis (2-oxazoline), 2,2'-p-phenylene bis (4-methyl-2-oxazoline), 2,2'-p-phenylene bis (4,4-dimethyl-2-oxazoline), 2,2'-m-phenylene bis (4-methyl-2-oxazoline), 2,2'-m -Phenylene bis (4,4-dimethyl-2-oxazoline), 2,2'-ethylene bis (2-oxazoline), 2,2'-tetramethylene bis (2-oxazoline), 2,2 ' -Tetramethylenebis (4,4-dimethyl-2-oxazoline), 2,2'-9,9'-diphenoxyethanebis (2-oxazoline), 2,2'-cyclohexylenebis (2 -Oxazoline) and 2,2'-diphenyl Bis (2-oxazoline) at least one member, the flame-retardant polyester-based artificial hair, selected from the group consisting of a. The method according to any one of claims 1, 4 or 5, At least one compound (C) selected from the group consisting of a carbodiimide compound, a bisoxazoline compound and an isocyanate compound is 1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2, 4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, hydrogenated xyl Ethylene diisocyanate, p-phenylenedi isocyanate, tolylene diisocyanate, xylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI ), Triphenylmethane triisocyanate and at least one member selected from the group consisting of 4,4'-diphenylether diisocyanate, flame-retardant polyester type Artificial hair. The method according to any one of claims 1 to 8, A flame retardant polyester artificial hair in which the flame retardant polyester artificial hair is non-crimped silk thread. The method according to any one of claims 1 to 9, A flame-retardant polyester artificial hair in which a flame-retardant polyester artificial hair is original. The method according to any one of claims 1 to 10, A flame retardant polyester artificial hair having a short fiber fineness of 10 to 100 dtex of a flame retardant polyester artificial hair.