JP2006307356A - Fiber for artificial hair - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fiber for an artificial hair, decreasing the reduction of flame retardance of the fiber formed from a flame retardant polyester-based resin composition, and excellent in smoothness, comb-passing through property and shampoo resistance. <P>SOLUTION: This flame resistant fiber for the artificial hair is provided by attaching a non-silicone-based fiber-treating agent having a reactivity and consisting of a polyether-based compound containing a functional group having a reactivity and a curing agent, on the fiber formed from the flame retardant polyester-based resin composition for capable of imparting the smoothness and comb-passing through property and obtaining the flame retardant fiber for the artificial hair, decreasing the reduction of the flame retardant property and excellent in shampoo resistance. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a flame-retardant artificial hair fiber excellent in smoothness, combing property, flame retardancy and shampoo resistance.

  Various synthetic fiber filaments are used as artificial hair used in wigs, hair wigs, and the like. As materials for synthetic fiber filaments for artificial hair, vinyl chloride, modacrylic, polyester, nylon, and the like are widely used. Polyester fiber, polypropylene fiber, polyamide fiber and the like are insufficient in flame retardancy when used directly as artificial hair.

  Various attempts have been made to improve the flame retardancy of these synthetic fibers. For example, a method in which a flame retardant monomer containing a phosphorus atom is copolymerized with a polyester resin, for example, a phosphorus atom is a ring member. And a method of copolymerizing a phosphorus compound having good thermal stability (Patent Document 1), a method of copolymerizing carboxyphosphinic acid (Patent Document 2), and a compound containing or blending a phosphorus compound with a polyester containing polyarylate A method (Patent Document 3) has been proposed. For example, a polyester fiber copolymerized with a phosphorus compound has been proposed as an application of these flame retardant techniques to artificial hair (Patent Documents 4 and 5).

  When used as artificial hair, various silicone finishes are generally used to impart flexibility, smoothness and the like. For example, dimethylpolysiloxane, methylhydrogen polysiloxane, hydroxylated dimethylpolysiloxane, vinyl group-containing organopolysiloxane, epoxy group-containing organopolysiloxane, amino, to give flexibility, wrinkle resistance, elasticity and compression recovery Group-containing organopolysiloxane, ester group-containing organopolysiloxane, polyoxyalkylene-containing organopolysiloxane, and the like. Further, a treatment agent comprising a combination of alkoxysilanes and / or a polyacrylamide resin or a catalyst has been known.

  For example, a treating agent (Patent Document 6) comprising an organopolysiloxane containing at least two epoxy groups per molecule and an organopolysiloxane containing amino groups, hydroxyl-terminated organopolysiloxane, amino groups in one molecule A method using a treating agent (Patent Document 7) comprising an organopolysiloxane containing an alkoxy group and / or a partial hydrolyzate and a condensate thereof is disclosed.

  Further, a treating agent comprising an organopolysiloxane containing an epoxy group and an aminoalkyltrialkoxysilane (Patent Documents 8 and 9) is a triorganosiloxy group diorganopolyester having both ends containing two or more amino groups in one molecule. Siloxane (Patent Document 10) is described. In addition, there is a method using a treatment agent (Patent Document 11) comprising an aminopolysiloxane containing two or more amino groups in one molecule and an alkoxysilane containing one or more reactive groups such as amino groups and epoxy groups. Proposed.

However, although the fibers attached with these silicone-containing fiber treatment agents are improved in smoothness, combing, etc., since the silicone fiber treatment agent itself is flammable, non-flame retardant synthetic fibers are flammable. However, the problem that the flame retardancy is remarkably lowered with respect to the flame retardant synthetic fiber remains.
Japanese Patent Publication No. 55-41610 Japanese Patent Publication No.53-13479 Japanese Patent Laid-Open No. 11-124732 JP-A-3-27105 JP-A-5-339805 Japanese Patent Publication No. 43-17514 Japanese Patent Publication No.53-36079 Japanese Patent Publication No.53-197159 Japanese Patent Publication No.53-19716 Japanese Patent Publication No. 53-98499 Japanese Patent Publication No.58-17310

  Provided is a fiber for artificial hair, which reduces a decrease in flame retardancy of a fiber formed from a flame retardant thermoplastic resin composition and is excellent in smoothness, combing resistance and shampoo resistance.

As a result of intensive studies to overcome the above-mentioned problems, the present inventors have achieved smoothness by attaching a reactive non-silicone fiber treatment agent to fibers formed from a flame-retardant thermoplastic resin composition. It has been found that a fiber for flame retardant artificial hair that can be imparted with properties and combing properties and reduced in flame retardancy can be maintained even when washed with shampoo or the like. That is, the present invention relates to a fiber for artificial hair obtained by attaching a reactive non-silicone fiber treatment agent (B) to a fiber formed from a composition comprising a flame retardant thermoplastic resin composition (A). (A)
The total adhesion amount of the fiber treatment agent (B) is 0.01 to 1% by weight with respect to the fibers formed from the components, and preferably the component (A) is thermoplastic. A polyester resin comprising a resin (A1), a flame retardant (A2), and a flame retardant aid (A3), and each component ratio is 100% by weight of (A1), (A2) and (A3). (A1) 90 to 65% by weight, flame retardant (A2) 10 to 25% by weight and flame retardant aid (A3) 0 to 10% by weight, and the thermoplastic resin (A1) is polyester. , At least one selected from the group consisting of polyamide and polyolefin, and the flame retardant (A2) is a phosphate compound, a phosphonate compound, a phosphinate compound, a phosphine oxide compound, a phosphat Compound, phosphonite compound, phosphinite compound, phosphine compound, condensed phosphate ester compound, organic cyclic phosphorus compound, bromine-containing phosphate ester flame retardant, brominated polystyrene flame retardant, brominated benzyl acrylate flame retardant, Brominated epoxy flame retardant, brominated phenoxy flame retardant, brominated polycarbonate flame retardant, tetrabromobisphenol A derivative, bromine-containing triazine compound and bromine-containing isocyanuric acid compound are at least one kind, The flame retardant aid (A3) is at least one selected from the group consisting of melamine cyanurate, antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium antimonate, zinc borate, zinc stannate and zinc hydroxystannate. Yes, thermoplastic resin group Object (A) limiting oxygen index of (LOI) is an artificial hair fibers is 25 or more. More preferably, the reactive non-silicone fiber treatment agent (B) comprises a polyether-based compound (B1) containing a reactive functional group and a curing agent (B2), and each component ratio is (B1) / (B2) = 100/0 to 50/50, and the polyether compound (B1) is a polyoxyethylene skeleton, a polyoxypropylene skeleton, and a polyoxyethylene -One or more having a skeleton selected from the group consisting of a random copolymer skeleton or a block copolymer skeleton of polyoxypropylene, and as a reactive functional group, from a group consisting of a hydroxyl group, an epoxy group, an amino group and an alkoxysilyl group It has one or more functional groups selected, and the curing agent (B2) is an epoxy group, an amino group or an isocyanate group. Compounds having at least two reactive groups selected from the group consisting and / or to fibers for artificial hair is a silane coupling agent.

  Moreover, it is preferable that an anionic and / or cationic antistatic agent is attached to the artificial hair fiber.

  According to the present invention, in a fiber formed from a flame retardant thermoplastic resin composition, a flame retardant artificial hair fiber excellent in smoothness, combing property, flame resistance and shampoo resistance can be obtained.

  The fiber for artificial hair of the present invention is a fiber for artificial hair formed by attaching a reactive non-silicone fiber treatment agent (B) to a fiber formed from the flame-retardant polyester resin composition (A). is there.

  It is difficult for the flame retardant thermoplastic resin composition (A) used in the present invention to be a flame retardant polyester composed of a thermoplastic resin (A1), a flame retardant (A2), and a flame retardant aid (A3). It is preferable from the point of the property as a flammability, a fiber physical property, and artificial hair.

  The thermoplastic resin (A1) used in the present invention is not particularly limited as long as it is a resin suitable for spinning artificial hair fibers of 10 to 100 dtex. As the thermoplastic resin (A), polyalkylene terephthalate, polyolefin, and polyamide are preferable from the viewpoint of characteristics as artificial hair.

  Examples of the polyalkylene terephthalate, polyolefin, and polyamide contained in the thermoplastic resin (A) of the present invention include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, 6-nylon, 6,6-nylon and the like, each of which is not necessarily a single polymer, and may be a blend polymer or copolymer. Among these, polyethylene terephthalate is preferable from the viewpoints of heat resistance, fiber properties, availability, and low cost.

  There is no limitation in particular in the flame retardant (A2) used for this invention, If it is a phosphorus containing flame retardant generally used and a halogen containing flame retardant, it can be used. Specific examples of the phosphorus-containing flame retardant include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, Tris (phenylphenyl) phosphate, trinephtyl phosphate, cresylphenyl phosphate, xylenyl diphenyl phosphate, triphenylphosphine oxide, tricresylphosphine oxide, methanephosphonic acid diphenyl, phenylphosphonic acid diethyl, and resorcinol polyphenyl Phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate Fate, hydroquinone poly (2,6-xylyl) phosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-methacryloyloxyethyl phosphate, tris (3 -Hydroxypropyl) phosphine, tris (4-hydroxybutyl) phosphine, tris (3-hydroxypropyl) phosphine oxide, tris (3-hydroxybutyl) phosphine oxide, 3- (hydroxyphenylphosphinoyl) propionic acid and the like. .

  Specific examples of the halogen-containing flame retardant include, for example, pentabromotoluene, hexabromobenzene, decabromodiphenyl, decabromodiphenyl ether, bis (tribromophenoxy) ethane, tetrabromophthalic anhydride, ethylenebis (tetrabromophthalimide), ethylene Bromine-containing phosphate esters such as bis (pentabromophenyl), octabromotrimethylphenylindane, tris (tribromoneopentyl) phosphate, brominated polystyrenes, brominated polybenzyl acrylates, brominated epoxy oligomers, brominated Polycarbonate oligomers, tetrabromobisphenol A, tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (allylamine) ), Tetrabromobisphenol A-bis (hydroxyethyl ether), tetrabromobisphenol A derivatives, bromine-containing triazine compounds such as tris (tribromophenoxy) triazine, bromine such as tris (2,3-dibromopropyl) isocyanurate Examples thereof include isocyanuric acid-based compounds.

  Among these, a flame retardant having a melting point of 100 ° C. or higher, more preferably 160 ° C. or higher is preferable from the viewpoint of heat resistance and fiber property deterioration suppression, and a halogen-based flame retardant is used from the viewpoint of flame retardant strength. It is preferable to do this.

  Among halogen flame retardants, bromine-containing phosphate ester flame retardant, brominated polystyrene flame retardant, brominated benzyl acrylate flame retardant, brominated polycarbonate flame retardant, brominated epoxy flame retardant, tetrabromobisphenol A Derivatives, brominated triazine-based compounds, and bromine-containing isocyanuric acid-based compounds are preferable, and brominated phosphate-based flame retardants and brominated epoxy-based flame retardants are more preferable in terms of transparency and color developability.

  The flame retardant (A3) used in the present invention is not particularly limited, and any flame retardant aid that is generally used can be used. Specific examples of the flame retardant aid include melamine cyanurate, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate and the like. These may be surface-treated with an epoxy compound, a silane compound, an isocyanate compound, a titanate compound or the like as necessary.

  The component ratio of the thermoplastic resin (A1), the flame retardant (A2), and the flame retardant aid (A3) in the flame retardant polyester resin composition of the present invention is (A1), (A2) and (A3). When the total amount is 100% by weight, it is preferable that the thermoplastic resin (A1) is 90 to 65% by weight, the flame retardant (A2) is 10 to 25% by weight, and the flame retardant aid (A3) is 0 to 10% by weight. (A1) 90 to 75% by weight, (A2) 10 to 20% by weight, and (A3) 1 to 5% by weight, more preferably (A1) 85 to 80% by weight, (A2) 12 to 15% by weight. % And (A3) are more preferably 3 to 5% by weight. When the amount of the polyester-based resin (A1) is more than 90% by weight, the flame retardant (A2) and the flame retardant auxiliary (A3) content tend to be low, so that sufficient flame retardancy tends not to be obtained. When the amount is less than 65% by weight, heat resistance and fiber physical properties tend to decrease. When the amount of the flame retardant (A2) is less than 10% by weight, the flame retardancy tends to be insufficient, and when it is more than 25% by weight, the heat resistance and the fiber physical properties tend to decrease. When the amount of the flame retardant aid (A3) is more than 10% by weight, the processing stability, drip resistance, fiber properties, and the hue of the polyester fiber tend to decrease.

  In the present invention, the limiting oxygen index (LOI) of the flame retardant thermoplastic resin composition (A) is preferably 25 or more, and more preferably 28 or more. When the limiting oxygen index (LOI) is less than 25, there is a tendency that sufficient flame retardancy cannot be obtained.

  In the present invention, the non-silicone fiber treatment agent (B) having reactivity is attached to the fiber (A) molded from the flame-retardant thermoplastic resin composition, thereby providing a tactile sensation, combing, and shampoo resistance. Can be granted.

  The non-silicone fiber treatment agent (B) used in the present invention is composed of a polyether compound (B1) containing a reactive functional group and a curing agent (B2). The ratio is preferably (B1) / (B2) = 100/0 to 50/50, more preferably 95/5 to 60/40, and still more preferably 90/10 to 70/30. When the component ratio of the curing agent (B2) is larger than 50, the tactile sensation and combing tend to be lowered.

  There is no limitation in particular in the polyether type compound (B1) containing the functional group which has the reactivity used for this invention, The polyoxyethylene frame | skeleton represented by General formula (1)-(4), a polyoxypropylene frame | skeleton, Any compound having a random copolymer skeleton or a block copolymer skeleton of polyoxyethylene-polyoxypropylene can be used.

(Wherein k represents an integer of 15 to 300)

(In the formula, m represents an integer of 15 to 200)

(In the formula, n and p each represent an integer of 10 to 200, and the ratio is n / p = 5/95 to 95/5 in molar ratio)

(In the formula, q, r and s each represent an integer of 10 to 150, and the ratio is q / r / s = 5/90/5 to 40/20/40 in terms of molar ratio).

  Examples of the reactive functional group of the polyether compound (B1) used in the present invention include functional groups such as a hydroxyl group, an epoxy group, an amino group, and an alkoxysilyl group.

  In order to obtain a polyether compound (B1) containing a functional group having reactivity, a compound having these functional groups is added to a random copolymer of polyoxyethylene skeleton, polyoxypropylene skeleton, and polyoxyethylene-polyoxypropylene. What is necessary is just to make it react with the polyether which has a polymerization skeleton or a block copolymer skeleton.

  As the polyether compound (B1) containing a reactive functional group used in the present invention, polyethylene glycol, polypropylene glycol, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether are preferable in terms of touch and combing. .

  As the curing agent (B2) used in the present invention, any compound or silane coupling agent having at least two reactive groups selected from the group consisting of an epoxy group, an amino group and an isocyanate group can be used. . Specific examples of the curing agent (B2) include, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, Tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether, bis (4- Hydroxyphenyl) methane diglycidyl ether, 1,1-bis (4-hydroxyphenyl) ethanediglycidyl ether 2,2-bis (4-hydroxycyclohexyl) propane diglycidyl ether, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl diglycidyl ether, 2,2'-bis (4- (Β-Hydroxypropoxy) phenyl) propanediglycidyl ether, 3,4-epoxycyclohexylmethyl, 3,4-epoxycyclohexanecarboxylate, compounds having an epoxy group such as vinylcyclohexene dioxide, ethylenediamine, 1,3-propylenediamine , Tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, paraxylylenediamine, 2,2,4-trimethylhexa Compounds having amino groups such as methylenediamine, 2,4,4-trimethylhexamethylenediamine, 3-methylpentamethylenediamine, 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'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, p-phenylene diisocyanate, tolylene diisocyanate , Xylylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate Triphenylmethane triisocyanate, a compound having an isocyanate group, such as 4,4'-diphenyl ether diisocyanate, amino group-containing silane coupling agents, silane coupling agents such as epoxy group-containing silane coupling agent.

  As the curing agent (B2) used in the present invention, an aliphatic compound is preferable from the viewpoint of touch and combing property.

  In the fiber for artificial hair of the present invention, the amount of the non-silicone fiber treatment agent (B) having reactivity is based on the weight of the fiber formed from the flame-retardant polyester resin composition (A). 0.01 to 1% is preferable, and 0.05 to 0.6% is more preferable. When the adhesion amount of the non-silicone fiber treatment agent (B) having reactivity is less than 0.01%, the effect of the fiber treatment agent is insufficiently exhibited, so that the smoothness and combing property of the fiber cannot be obtained. If the adhesion amount is more than 1%, the fiber treatment agent may become excessive, resulting in a sticky feeling or troubles during processing such as eyelashes.

Further, in order to impart antistatic properties and the like, it is preferable to use a hydrophilic fiber treatment agent, and any hydrophilic fiber treatment agent that is generally used can be used. Specific examples of hydrophilic fiber treatment agents include polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl esters, polyoxyalkylene alkyl amines, N, N-dihydroxyethyl alkyl amides, polyoxyalkylene alkyl amides, polyglycerin fatty acid esters, poly Oxyalkylene pentaerythritol alkyl ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene, alkylamine salt, alkylammonium salt, alkylaralkylammonium salt, alkylpyridinium salt, alkylpicolinium salt, alkylsulfonate, alkylbenzenesulfonate, Alkyl naphthalene sulfonate, alkyl sulfo fatty acid ester salt, alkyl sulfate ester salt, alkenyl sulfate ester , Polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkyl ether carboxylates, polyoxyalkylene alkenyl ether sulfate, alkyl phosphate salts, and the like mixture of ionic surfactants.

The artificial hair fiber of the present invention is prepared by, for example, dry blending the components (A1), (A2) and (A3), and then, for example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, and various kinds of kneaders. The composition obtained by melt kneading using a kneader can be produced by melt spinning by a normal melt spinning method. That is, for example, the temperature of an extruder, a gear pump, a die, etc. is set to 270 to 310 ° C., melt-spun, the spun yarn is passed through a heating tube, cooled to the glass transition point or lower, and 50 to 5000 m / min. A spun yarn is obtained by pulling at a speed of. It is also possible to control the fineness by cooling the spun yarn in a water tank containing cooling water. The temperature and length of the heating cylinder, the temperature and blowing amount of the cooling air, the temperature of the cooling water tank, the cooling time, and the take-up speed can be appropriately adjusted depending on the discharge amount and the number of holes in the die.

The obtained spun yarn is hot-drawn, but the drawing is performed by winding the spun yarn once and then drawing 2
Any of a process method and a direct spinning drawing method in which drawing is performed continuously without winding 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 heat-resistant agents, light stabilizers, fluorescent agents, antioxidants, antistatic agents, pigments, plasticizers, and lubricants as necessary. Can do. By incorporating a pigment, a primary fiber can be obtained.

When the polyester-based artificial hair of the present invention is priming, it can be used as it is, but when it is not priming, it can be dyed under the same conditions as ordinary polyester-based fibers. As pigments, dyes, auxiliaries and the like used for dyeing, those having good weather resistance and flame retardancy are preferable.

  In the present invention, the fiber formed from the flame retardant polyester resin composition (A) is made of a random or block copolymer containing an aliphatic or aromatic (poly) ester segment and a (poly) ether segment. The method for attaching the fiber treatment agent (B) is not particularly limited, and the fiber treatment agent (B) can be treated by a known method. For example, an aqueous solution containing the fiber treatment agent of the present invention is prepared, a tow filament having a total fineness of 100,000 dtex is immersed, and squeezed so that the liquid content is 20 to 30% with respect to the tow weight, and a predetermined amount (% omf The fiber treatment agent can be adhered so that the fiber treatment agent is attached and dried at 130 ° C. for 10 minutes using a hot air dryer. In addition, stretching and heat treatment are performed, followed by immersion in an aqueous solution containing a fiber treatment agent, squeezing so that the liquid content is 20 to 30% with respect to the tow weight, and a predetermined amount (% omf) of the fiber treatment agent is adhered. The fiber treatment agent can be adhered by allowing the solution to adhere and drying. Moreover, it can also be made to adhere to a fiber using a fixed amount supply apparatus.

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.

The artificial hair of the present invention may be used in combination with other artificial hair materials such as modacrylic fiber and polyvinyl chloride fiber, or may be used 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.

(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 hung vertically, and a 20 mm flame is applied to the fixed filament with an effective length of 120 mm for 3 seconds. Indirect flames were burned and evaluated.
-Flame resistance-
A: After flame time is 0 seconds (no ignition)
○: After-flame time is less than 3 seconds Δ: After-flame time is 3 seconds or more and less than 10 seconds X: 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).

(Comb street)
A fiber surface treatment agent is attached to a tow filament having a length of 30 cm and a total fineness of 100,000 dtex. 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

(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 stickiness and slip on the filament surface.
◎: There is a smooth feeling ○: There is no stickiness △: There is a little sticky feeling ×: There is a sticky feeling

(Shampoo resistance)
Rinse the tow filament with a length of 30 cm and a total fineness of 100,000 dtex with 40 ° C warm water to 5% by adding a normal shampoo (such as Sara: Kanebo Co., Ltd.) that does not contain a commercial rinse. The process of natural drying is performed for 3 cycles, and the change in characteristics before and after cleaning (tactile feeling, combing) is evaluated (characteristic retention). In addition, the amount of the fiber treatment agent attached before and after washing is measured and used as a measure of shampoo resistance.
-Property retention-
◎: No change in characteristics ○: Little change △: Some change ×: Change -Fiber treatment agent adhesion amount-
The adhesion amount before and after cleaning was calculated by the following formula. A thing with a large change of the adhesion amount of a fiber treatment agent before and behind washing | cleaning shows that shampoo resistance is low.
1) (Adhesion amount before cleaning:% omf) = [(weight after adhesion of fiber treatment agent) − (weight before adhesion of fiber treatment agent)] / (weight before adhesion of fiber treatment agent) × 100
2) (Adhesion amount after washing:% omf) = [(Weight after washing) − (Weight before adhesion of fiber treatment agent)] / (Weight before adhesion of fiber treatment agent) × 100

(Antistatic property)
A tow filament with a length of 30 cm and a total fineness of 100,000 dtex, room temperature 25 ° C., humidity 40%
After standing in a constant temperature and humidity chamber for 24 hours, hold the top of the tow filament in one hand and hang it vertically, and insert a comb (NEW DELRIN COMB No. 826) 3 cm above the tow filament at a speed of 0.3 m / s. From here, the state of the tow filament is observed when it is passed 30 times or more to the lower end of the tow filament.
A: No change (Tow does not spread because there is no static charge)
○: Several filaments spring outward △: Dozens of filaments spring outward due to static electricity ×: Spreads overall due to static electricity

The raw materials used in the examples and comparative examples are as follows.
Thermoplastic resin (A1):
-Polyethylene terephthalate, Kanebo Gosei Co., Ltd., EFG-85A
-Polypropylene, manufactured by Nippon Polychem Co., Ltd., Novatec PP
・ Nylon 66, manufactured by Unitika Ltd., Maranyl nylon 66 A226
Flame retardant (A2):
-Brominated phosphate ester flame retardant, manufactured by Daihachi Chemical Industry Co., Ltd., CR-900
-Brominated epoxy flame retardant, Sakamoto Pharmaceutical Co., Ltd., SR-T20000
Flame retardant aid (A3):
・ Sodium antimonate, manufactured by Nippon Seiko Co., Ltd., SA-A, average particle size 2.5 μm
-Antimony trioxide, manufactured by Nippon Seiko Co., Ltd., PATOX-P, average particle size 3 μm
Curing agent (B2):
Aliphatic amine compound, manufactured by Three Bond Co., Ltd., ThreeBond 2103
・ Γ- (2-aminoethyl) aminopropyltrimethoxysilane, manufactured by Toray Dow Corning Co., Ltd., SH6020
Hydrophilic fiber treatment agent:
・ Cationic surfactant, manufactured by Maruhishi Oil Chemical Co., Ltd., processing agent No. 29
・ Ethylene oxide-propylene oxide copolymerized random polyether, manufactured by Maruhishi Oil Chemical Co., Ltd., KWC-Q
Silicone fiber treatment agent:
・ Amino-modified silicone fiber treatment agent; manufactured by Maruhishi Oil Chemical Co., Ltd., KWC-B

(Production Examples 1-4)
The composition shown in Table 1 was dried to a moisture content of 100 ppm or less, dry blended, supplied to a twin screw extruder, melt-kneaded, pelletized, and dried to a moisture content of 100 ppm or less.
Next, using a melt spinning machine, the molten polymer was discharged from a spinneret having 40 nozzle holes with a diameter of 1 mm, air-cooled with cooling air at 20 ° C., and wound at a speed of 100 m / min to obtain an undrawn yarn. .
The obtained undrawn yarn is stretched 4 times using a heated heat roll, heat-treated using a heated heat roll, wound up at a speed of 30 m / min, and a single fiber fineness of about 50 dtex is difficult. A fuel fiber (multifilament) was obtained.

(Production Example 5)
A four-necked flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, 100 parts by weight of ethylene oxide-propylene oxide copolymerized random polyether (KRE-15, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), epichlorohydrin 6 weights Part, 100 parts by weight of diethylene glycol dimethyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) and 0.2 parts by weight of triethylbenzylammonium chloride are added. While maintaining the temperature at 50 to 60 ° C., 0.8 part by weight of solid sodium hydroxide is added in portions over 1 hour, and further reacted at the same temperature for 8 hours. The produced salt is separated by washing and separating operations, and washing is repeated several times. Excess epichlorohydrin was distilled off under reduced pressure to obtain an ethylene oxide-propylene oxide copolymerized random polyether having glycidyl introduced at the terminal.

(Production Example 6)
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, 100 parts by weight of ethylene oxide-propylene oxide copolymerized random polyether (KRE-15, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), diethylene glycol dimethyl ether 70 The mixture of 2.5 parts by weight of 3-chloropropyltrimethoxysilane (KBM-703, manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts by weight of diethylene glycol dimethyl ether was charged at room temperature. Then, the solution is slowly dropped from the dropping funnel over 1 hour, and after completion of the dropping, the temperature is raised to 50 to 60 ° C. and reacted for 3 hours. Diethylene glycol dimethyl ether and excess 3-chloropropyltrimethoxysilane were distilled off under reduced pressure to obtain an ethylene oxide-propylene oxide copolymerized random polyether having an alkoxysilyl group introduced at the terminal.

(Examples 1-7)
Using the fibers obtained in Production Examples 1 to 4, an aqueous solution containing the fiber treatment agent shown in Table 2 was prepared, and a tow filament having a total fineness of 100,000 dtex was immersed therein, and the liquid content was 20 to 30 with respect to the tow weight. The solution was attached so that a predetermined amount (% omf) of the fiber treatment agent shown in Table 2 was adhered, and dried at 130 ° C. for 10 minutes using a hot air dryer.

  Table 3 shows the results of evaluation of flame retardancy, combing, tactile sensation, shampoo resistance, and antistatic properties of each artificial hair to which the fiber treatment agent was adhered.

(Comparative Examples 1 and 2)
Using the fibers obtained in Production Example 1, prepare an aqueous solution containing the fiber treatment agent shown in Table 2, soak tow filaments with a total fineness of 100,000 dtex, and a liquid content of 20 to 30% with respect to the tow weight. The solution was squeezed so that a predetermined amount (% omf) of the fiber treatment agent shown in Table 2 was adhered, and dried at 130 ° C. for 10 minutes using a hot air dryer.

  Table 3 shows the results of evaluation of flame retardancy, combing, tactile sensation, shampoo resistance, and antistatic properties of each artificial hair to which the fiber treatment agent was adhered.

  As shown in Table 3, compared with the comparative example, in the example, the decrease in flame retardancy is small and sufficient flame retardancy is exhibited, and the artificial property is excellent in combing property, touch feeling, shampoo resistance, and antistatic property. It was confirmed that a fiber for hair was obtained. Therefore, the artificial hair using the non-silicone fiber treatment agent (polyether fiber treatment agent) having the present reactivity introduces a functional group having reactivity and causes a crosslinking reaction with a curing agent, thereby producing a fiber ( Artificial hair) Sticks to the surface, and even if shampooed, the fiber treatment agent is difficult to remove and retains its characteristics. Compared to the case of using a normal non-reactive fiber treatment agent, it feels like a comb and feels shampoo resistant. It was confirmed that the film was excellent in the properties and antistatic properties.

Claims (17)

  A fiber for artificial hair obtained by adhering a reactive non-silicone fiber treatment agent (B) to a fiber formed from a flame-retardant thermoplastic resin composition (A).   The artificial amount according to claim 1, wherein the amount of the fiber treatment agent (B) attached is 0.01 to 1% by weight with respect to the weight of the fiber formed from the flame retardant thermoplastic resin composition (A). Fiber for hair.   The flame retardant thermoplastic resin composition (A) comprises a thermoplastic resin (A1), a flame retardant (A2), and a flame retardant aid (A3), and each component ratio is (A1), (A2) and When the total amount of (A3) is 100% by weight, the polyester resin (A1) is 90 to 65% by weight, the flame retardant (A2) is 10 to 25% by weight, and the flame retardant aid (A3) is 0 to 10% by weight. Item 3. An artificial hair fiber according to Item 1 or 2.   The fiber for artificial hair according to claim 3, wherein the thermoplastic resin (A1) is one or more polymers selected from the group consisting of polyester, polyamide, and polyolefin.   Flame retardant (A2) is phosphate compound, phosphonate compound, phosphinate compound, phosphine oxide compound, phosphite compound, phosphonite compound, phosphinite compound, phosphine compound, condensed phosphate ester compound, organic cyclic phosphorus compound , Bromine-containing phosphate ester flame retardant, brominated polystyrene flame retardant, brominated benzyl acrylate flame retardant, brominated epoxy flame retardant, brominated phenoxy flame retardant, brominated polycarbonate flame retardant, tetrabromobisphenol A The artificial hair fiber according to claim 3 or 4, which is at least one selected from the group consisting of a derivative, a bromine-containing triazine compound, and a bromine-containing isocyanuric acid compound.   The flame retardant aid (A3) is at least one selected from the group consisting of melamine cyanurate, antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium antimonate, zinc borate, zinc stannate and zinc hydroxystannate. The artificial hair fiber according to any one of claims 3 to 5.   The fiber for artificial hair according to any one of claims 3 to 6, wherein the flame retardant thermoplastic resin composition (A) has a limiting oxygen index (LOI) of 25 or more.   The reactive non-silicone fiber treatment agent (B) comprises a polyether-based compound (B1) containing a functional group having reactivity and a curing agent (B2). The fiber for artificial hair according to claim 1 or 2, wherein B1) / (B2) = 100/0 to 50/50.   The polyether compound (B1) is one or more having a skeleton selected from the group consisting of a polyoxyethylene skeleton, a polyoxypropylene skeleton, and a polyoxyethylene-polyoxypropylene random copolymer skeleton or a block copolymer skeleton. The artificial hair fiber according to claim 8, which is a compound.   The artificial compound according to claim 8 or 9, wherein the polyether compound (B1) has one or more functional groups selected from the group consisting of a hydroxyl group, an epoxy group, an amino group, and an alkoxysilyl group as a reactive functional group. Fiber for hair.   The artificial hair fiber according to any one of claims 8 to 10, wherein the polyether compound (B1) is polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether.   The fiber for artificial hair according to claim 8, wherein the curing agent (B2) is a compound having at least two reactive groups selected from the group consisting of an epoxy group, an amino group and an isocyanate group and / or a silane coupling agent. .   The compound having an epoxy group of the curing agent (B2) is ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether. , Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether, bis (4-hydroxyphenyl) methane diglycidyl ether and 2,2- The artificial hair according to claim 8 or 12, which is at least one selected from the group consisting of bis (4-hydroxycyclohexyl) propane diglycidyl ether. Fiber.   The compound having an amino group of the curing agent (B2) is ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine. 13, which is one or more selected from the group consisting of 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine and 3-methylpentamethylenediamine. Fiber for artificial hair.   The compound having an isocyanate group of the curing agent (B2) is 1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate. The artificial hair according to claim 8 or 12, which is at least one selected from the group consisting of, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and hydrogenated xylylene diisocyanate. fiber.   The fiber for artificial hair according to claim 8 or 12, wherein the silane coupling agent of the curing agent (B2) is at least one selected from the group consisting of an amino group-containing silane coupling agent and an epoxy group-containing silane coupling agent. .   An artificial hair fiber obtained by further attaching an anionic and / or cationic antistatic agent to the artificial hair fiber according to any one of claims 1 to 16.