JP2006307355A - 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 fiber-treating agent consisting of a random or block copolymer containing an aliphatic or aromatic polyester segment and a polyether segment 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 problems, the present inventor has found that the fibers formed from the flame-retardant polyester resin composition contain random or block co-polymers containing aliphatic or aromatic polyester segments and polyether segments. By attaching a fiber treatment agent composed of coalescence, it is possible to give smoothness and combing properties, and to obtain a fiber for flame retardant artificial hair with reduced flame retardancy. Even when washed with shampoo etc. It was found that the characteristics can be maintained.

That is, the present invention
Fiber treatment comprising a random or block copolymer containing an aliphatic or aromatic (poly) ester segment and a (poly) ether segment on a fiber formed from a composition comprising the flame retardant polyester resin composition (A) It is a fiber for artificial hair formed by adhering the agent (B), and the total amount of the fiber treatment agent (B) attached to the fiber formed from the flame retardant polyester resin composition (A) by weight ratio. It is a fiber for artificial hair that is 0.01 to 1%. Preferably, the flame-retardant polyester resin composition (A) comprises a polyester 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), polyester resin (A1) 90-65% by weight, flame retardant (A2) 10 5% by weight and flame retardant aid (A3) 0 to 10% by weight of artificial hair fiber, polyester resin (A1) is a type of copolymer polyester mainly composed of polyalkylene terephthalate and polyalkylene terephthalate The polyester comprising the above, the flame retardant (A2) is a phosphate compound, a phosphonate compound, a phosphinate compound, a phosphine oxide compound, a phosphite compound, a phosphonite compound, a phosphinite compound, a phosphine compound, condensed phosphoric acid 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, Tetra It is at least one selected from the group consisting of a lomobisphenol A derivative, a bromine-containing triazine compound and a bromine-containing isocyanuric acid compound, and the flame retardant aid (A3) is melamine cyanurate, antimony trioxide, antimony tetraoxide, five Artificial oxygen which is at least one selected from the group consisting of antimony oxide, sodium antimonate, zinc borate, zinc stannate and zinc hydroxystannate, and has a limiting oxygen index (LOI) of 25 or more in the polyester resin composition (A) It is a fiber for hair. More preferably, the fiber treatment agent (B) contains a (poly) ester segment represented by the following general formula (1) and a (poly) ether segment represented by the following general formula (2). Coalesced,

(In the formula, m represents an integer of 2 to 4, and n represents an integer of 1 to 100.)

(In the formula, R ¹ represents hydrogen or a methyl group, and p represents an integer of 1 to 200.)
It is related with the fiber for artificial hair whose weight average molecular weights of a fiber processing agent (B) are 1000-30000.

  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 random or block co-polymer containing an aliphatic or aromatic (poly) ester segment and a (poly) ether segment in the fiber formed from the flame-retardant polyester resin composition (A). It is a fiber for artificial hair to which a fiber treatment agent (B) made of coalescence is adhered.

  It is a fiber for artificial hair whose adhesion amount of the fiber treatment agent (B) is 0.01 to 1% by weight with respect to the fiber weight formed from the flame retardant polyester resin composition (A).

  The flame retardant polyester resin composition (A) is composed of a polyester 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, it is 90 to 65% by weight of the polyester resin (A1), 10 to 25% by weight of the flame retardant (A2), and 0 to 10% by weight of the flame retardant aid (A3).

  It is difficult for the flame retardant polyester resin composition (A) used in the present invention to be a flame retardant polyester composed of a polyester 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.

  There is no limitation in particular in the polyester-type resin (A1) used for this invention, What is necessary is just a resin suitable for spinning of 10-100 dtex artificial hair fiber. The polyester resin (A) is a polyester composed of at least one of polyalkylene terephthalate or a copolyester mainly composed of polyalkylene terephthalate. Examples of the polyalkylene terephthalate include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, etc., and each does not need to be a single polymer, but can be a blend polymer or copolymer polymer. There may be. Among these, polyethylene terephthalate is preferable from the viewpoint 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 or 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, for example, melamine cyanurate, antimony trioxide, antimony tetraoxide, 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, if necessary.

  In the flame retardant polyester resin composition of the present invention, the component ratio of the polyester resin (A1), the flame retardant (A2) and the flame retardant auxiliary (A3) is (A1), (A2) and (A3). When the total is 100% by weight, it is preferably 90 to 65% by weight of the polyester resin (A1), 10 to 25% by weight of the flame retardant (A2) and 0 to 10% by weight of the flame retardant aid (A3). (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 flame-retardant thermoplastic composition of the present invention, as the polyester resin (A1), polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate are preferable from the viewpoint of fiber properties and properties as artificial hair, and (A2) The combination with (A3) includes a combination of a condensed phosphate ester compound and / or an organic cyclic phosphorus compound and melamine cyanurate, a bromine-containing phosphate ester flame retardant and / or a brominated epoxy flame retardant and antimony trioxide. And / or a combination with sodium antimonate is preferable from the viewpoint of flame retardancy and fiber hue.

  In the present invention, the limiting oxygen index (LOI) of the flame retardant polyester 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, a fiber made of a random or block copolymer containing an aliphatic or aromatic (poly) ester segment and a (poly) ether segment in the fiber (A) molded from the flame-retardant polyester resin composition By attaching the treatment agent (B), shampoo resistance can be imparted according to the feel and comb.

  The fiber treatment agent (B) comprising a random or block copolymer containing an aliphatic or aromatic (poly) ester segment and (poly) ether segment used in the present invention includes (poly) ester segment and (poly) ether. Any compound formed from a random or block copolymer containing segments can be used.

  Specific examples of the (poly) ester segment in the fiber treatment agent (B) of the present invention include, for example, (poly) glycolide, (poly) caprolactone, (poly) pivalolactone, sebacic acid, adipic acid, phthalic acid, and the like. And aromatic (poly) esters represented by the general formula (1) such as (poly) ethylene terephthalate, (poly) ethylene terephthalate, (poly) propylene terephthalate, and (poly) butylene terephthalate. Among these, those having an aromatic polyester segment represented by the general formula (1) are preferable from the viewpoint of strong affinity with polyester fibers and excellent shampoo resistance.

  Specific examples of the (poly) ether segment in the fiber treatment agent (B) of the present invention include, for example, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol and the like. Examples include (poly) ethers composed of diols, (poly) ethylene glycol-based, (poly) propylene glycol-based (poly) ethers represented by the general formula (2), and random or block copolymers thereof. . Among these, what has a polyether segment represented by General formula (2) is preferable from a tactile sensation and a comb point.

  1000-30000 are preferable, as for the weight average molecular weight of the fiber processing agent (B) used for this invention, 2000-25000 are more preferable, and 3000-20000 are more preferable. When the weight average molecular weight of the fiber treatment agent (B) is less than 1000, the fiber treatment agent has a high viscosity, and therefore there is a tendency that the smoothness and combing property of the fiber cannot be obtained. In other words, the interaction (affinity) with the fiber is lowered, so that shampoo resistance tends not to be sufficiently exhibited.

  The amount of the fiber treatment agent (B) comprising a random or block copolymer containing an aliphatic or aromatic (poly) ester segment and a (poly) ether segment in the artificial hair fiber of the present invention is a flame-retardant polyester. 0.01 to 1% is preferable by weight ratio with respect to the weight of the fiber formed from a resin composition (A), and 0.05 to 0.6% is more preferable. When the amount of the fiber treatment agent (B) comprising a random or block copolymer containing an aliphatic or aromatic (poly) ester segment and a (poly) ether segment is less than 0.01%, the effect of the fiber treatment agent Insufficient expression tends to prevent fiber smoothness and combability from being obtained. When the amount exceeds 1%, the fiber treatment agent becomes excessive, causing a sticky feeling or when processing eyelashes, etc. May cause trouble.

  In the fiber for artificial hair of the present invention, it is preferable to use a hydrophilic fiber treating agent in order to impart antistatic properties and the like.

  As the hydrophilic fiber treatment agent in the present invention, any hydrophilic fiber treatment agent that is generally used can be used. Specific examples of the hydrophilic fiber treating agent include, for example, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl ester, polyoxyalkylene alkylamine, N, N-dihydroxyethyl alkylamide, polyoxyalkylene alkylamide, polyglycerin fatty acid ester. , Polyoxyalkylene pentaerythritol alkyl ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene, alkylamine salt, alkylammonium salt, alkylaralkylammonium salt, alkylpyridinium salt, alkylpicolinium salt, alkylsulfonate, alkylbenzenesulfonic acid Salt, alkyl naphthalene sulfonate, alkyl sulfo fatty acid ester salt, alkyl sulfate ester salt, alkenyl sulfate Ester salts, 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 obtained by, for example, dry blending the components (A1), (A2) and (A3) and then melt-kneading the composition using various general kneaders. It can be produced by melt spinning by a normal melt spinning method.

  Examples of the kneader used for the production of the resin composition include, for example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, and a kneader. Among these, a twin screw extruder is preferable from the viewpoint of adjusting the degree of kneading and ease of operation.

  For example, using a twin screw extruder with a screw diameter of 45 mm, the cylinder temperature is 260 to 300 ° C., the discharge amount is 50 to 150 kg / hr, the melt is kneaded at a screw rotation speed of 150 to 200 rpm, the strand is taken out from the die, and water-cooled. Later, the composition of the present invention can be obtained by pelletizing with a strand cutter.

  When the fiber for artificial hair of the present invention is melt-spun by a normal melt-spinning method, for example, the temperature of an extruder, a gear pump, a base, etc. is set at 270 to 310 ° C., melt-spun, and the spun yarn is heated. After passing through the tube, the yarn is cooled below the glass transition point and taken up at a speed of 50 to 5000 m / min to obtain a spun yarn. It is also possible to control the fineness by cooling the spun yarn in a water tank containing cooling water. The temperature and length of the heating cylinder, the temperature and blowing amount of the cooling air, the temperature of the cooling water tank, the cooling time, and the take-up speed can be appropriately adjusted depending on the discharge amount and the number of holes in the die.

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

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

  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 warm water of 40 ° C 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 was performed for 3 cycles. Evaluate changes in characteristics before and after cleaning (tactile feel, combing) (characteristic retention). Also, the amount of the fiber treatment agent attached before and after washing is measured and used as a measure of shampoo resistance.
-Property retention-
◎: There is no change in characteristics. ○: There is almost no change. △: There is a slight change.
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 processing 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.
Polyester (A1):
-Polyethylene terephthalate, manufactured by Mitsubishi Chemical Corporation, BK-2180
Flame retardant (A2):
-Brominated epoxy flame retardant, Sakamoto Pharmaceutical Co., Ltd., SR-T20000
・ Cyclic organophosphorus compound, Sanko Co., Ltd., SANKO-BCA
Flame retardant aid (A3):
・ Sodium antimonate, manufactured by Nippon Seiko Co., Ltd., SA-A
Inorganic fine particles:
・ Fine silica, manufactured by Fuji Silysia Chemical Co., Ltd., Silicia 310P
Pigment:
-Pigment master batch, carbon black 20wt%, manufactured by Dainichi Seika Kogyo Co., Ltd., PESM22367BLACK
Textile treatment agent:
Silicone fiber treatment agent:
・ Amino-modified silicone fiber treatment agent; manufactured by Maruhishi Oil Chemical Co., Ltd., KWC-B
Hydrophilic fiber treatment agent:
・ Cationic surfactant, manufactured by Matsumoto Yushi Seiyaku Co., Ltd., KRE-103
-Ethylene oxide-propylene oxide copolymerized random polyether, manufactured by Matsumoto Yushi Seiyaku Co., Ltd., KRE-102

(Production Examples 1 to 3)
A composition having a blending ratio shown in Table 1 is dried to a water content of 100 ppm or less, dry blended, supplied to a twin screw extruder (manufactured by Nippon Steel Works, TEX44), and melt kneaded at a cylinder set temperature of 280 ° C. And pelletized, and then dried to a moisture content of 100 ppm or less.
Next, using a melt spinning machine (SV30, manufactured by Shinko Machinery Co., Ltd.), the molten polymer is discharged from a spinneret having a round sectional nozzle hole with a nozzle diameter of 0.5 mm at a barrel set temperature of 280 ° C., and cooling air at 20 ° C. And then wound up at a speed of 100 m / min to obtain an undrawn yarn. The obtained unstretched yarn is stretched 4 times using a heat roll heated to 85 ° C., heat treated using a heat roll heated to 200 ° C., wound at a speed of 30 m / min, and single fiber A polyester fiber (multifilament) having a fineness of about 50 dtex was obtained.

(Production Examples 4 to 7)
Dimethyl terephthalate, ethylene glycol, polyethylene glycol, and polypropylene glycol were charged into a transesterification can at the ratio shown in Table 2, 0.06 part of calcium acetate monohydrate was added, and the temperature was changed from 140 ° C. to 230 ° C. over 4 hours in a nitrogen gas atmosphere. The ester exchange reaction was carried out while distilling out the glycol generated by raising the temperature to 0 ° C. Subsequently, calcium diester phosphate obtained by reacting 0.5 parts trimethyl phosphate and 0.3 parts calcium acetate monohydrate in 8.5 parts ethylene glycol at 120 ° C. for 60 minutes under total reflux. 0.57 parts of calcium acetate monohydrate was dissolved in the salt solution and transferred to a polymerization can with 0.04 parts of antimony trioxide. Subsequently, the pressure was reduced to 4 KPa over 1 hour, and at the same time, the temperature was raised from 230 ° C. to 275 ° C. over 1 hour. Under a reduced pressure of 133 Pa or less, polycondensation was performed at a polymerization temperature of 275 ° C. to obtain a copolymer.

(Production Example 8)
Dimethyl terephthalate, ethylene glycol, and triethylene glycol were charged into a transesterification can at the ratio shown in Table 2, and a transesterification reaction was performed in the same manner as in Production Examples 4 to 7. Subsequently, it was transferred to a polymerization can in the same manner, and the pressure was reduced to 4 KPa over 1 hour, and at the same time, the temperature was raised from 230 ° C. to 250 ° C. over 1 hour. Under a reduced pressure of 133 Pa or less, polycondensation was performed at a polymerization temperature of 250 ° C. to obtain a copolymer.

(Examples 1-8)
Using the fibers obtained in Production Examples 1 to 3, an aqueous solution containing the fiber treatment agent shown in Table 3 was prepared, and a tow filament having a total fineness of 100,000 dtex was immersed, 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 4 shows the results of evaluating the flame retardancy, combing, tactile sensation, shampoo resistance, and antistatic property of each fiber to which the fiber treatment agent was adhered.

(Comparative Examples 1-3)
Using the fibers obtained in Production Example 1, prepare an aqueous solution containing the fiber treatment agent shown in Table 3, 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 4 shows the results of evaluating the flame retardancy, combing, tactile sensation, shampoo resistance, and antistatic property of each fiber to which the fiber treatment agent was adhered.

  As shown in Table 4, with respect to 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 fiber treatment agent (B) comprising a random or block copolymer containing an aliphatic or aromatic polyester segment and a polyether segment is added to the fiber (A) molded from the flame retardant polyester resin composition of this time. The used fiber for artificial hair can be removed even when shampooed by introducing a polyester segment into the fiber treatment agent to increase the affinity and interaction between the fiber treatment agent and the flame retardant fiber. It was difficult to maintain characteristics and was confirmed to be superior in terms of combability, tactile sensation, shampoo resistance, and antistatic properties as compared with the case of using a normal silicone fiber treatment agent.

Claims (10)

  Fiber treatment agent (B) comprising a random or block copolymer containing an aliphatic or aromatic (poly) ester segment and a (poly) ether segment in the fiber formed from the flame retardant polyester resin composition (A) A fiber for artificial hair made by adhering.   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 polyester resin composition (A) is composed of a polyester 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 artificial hair fiber according to claim 3, wherein the polyester resin (A1) is a polyester composed of at least one of a polyalkylene terephthalate and a copolyester mainly composed of polyalkylene terephthalate.   Flame retardant (A2) is phosphate compound, phosphonate compound, phosphinate compound, phosphine oxide compound, phosphite compound, phosphonite compound, phosphinite compound, phosphine compound, condensed phosphate 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 fiber treatment agent (B) is a random or block copolymer containing a (poly) ester segment represented by the following general formula (1) and a (poly) ether segment represented by the following general formula (2): Item 3. The artificial hair fiber according to Item 1 or 2.

(In the formula, m represents an integer of 2 to 4, and n represents an integer of 1 to 100.)

(In the formula, R ¹ represents hydrogen or a methyl group, and p represents an integer of 1 to 200.)   The fiber for artificial hair according to claim 1, 2, or 8, wherein the fiber treatment agent (B) has a weight average molecular weight of 1,000 to 30,000.   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 9.