Polyacrylonitrile-based artificial hair fiber, and hair ornament product

Abstract

A polyacrylonitrile-based artificial hair fiber including a hair bundle of polyacrylonitrile-based artificial hair fibers having an excellent pulling property with water repellency maintained, and a hair ornament product including the fiber are provided. The polyacrylonitrile-based artificial hair fiber includes a polyacrylonitrile-based synthetic fiber (A), and an alkyl (meth)acrylate-based water repellent (B), a modified silicone (C) having an amino group, and an ionic antistatic agent (D) adhered to the polyacrylonitrile-based synthetic fiber (A). The alkyl (meth)acrylate-based water repellent (B) does not have a fluoro group. The alkyl (meth)acrylate-based water repellent (B) has a long-chain hydrocarbon side chain. A total adhesion amount of the alkyl (meth)acrylate-based water repellent (B), the modified silicone (C) having an amino group, and the ionic antistatic agent (D) is 0.1% omf or more and 0.4% omf or less with respect to an entire mass of the polyacrylonitrile-based synthetic fiber (A).

Description

TECHNICAL FIELD

[0001] One or more embodiments of the present invention relate to a polyacrylonitrile-based artificial hair fiber, and a hair ornament product.BACKGROUND

[0002] Conventionally, a fluorine-based water repellent having a fluorine-containing group has been known, and a fiber product having a surface provided with water repellency by treating the fiber product or the like with such a fluorine-based water repellent has been known. Such a fluorine-based water repellent is generally manufactured by polymerizing or copolymerizing a monomer having a fluoroalkyl group. A fiber product treated with the fluorine-based water repellent exhibits excellent water repellency, but a monomer having a fluoroalkyl group is less likely to be decomposed, and therefore places a large burden on the environment. Under such circumstances, in recent years, studies have been made on a non-fluorine-based water repellent including no fluorine. For example, Patent Document 1 mentions that an artificial hair fiber obtained by treating a polyacrylonitrile-based synthetic fiber with an alkyl acrylate-based water repellent is excellent in water repellency and a sense of touch.

[0003] Patent Document 1: PCT International Publication No. WO2023 / 190760

[0004] When processing is carried out using the artificial hair fibers disclosed in Patent Document 1, for example, it is assumed that a hair bundle of the artificial hair fibers packed in a corrugated cardboard box is pulled out, hooked to parallel bars or the like at a predetermined height constituting a processing machine, and the hair bundle is pulled out at a predetermined speed. When the hair bundle is pulled out and processed by such a method, the bundle of fibers is required to be pulled out continuously without tangling, but it has been found that when the hair bundle of the artificial hair fibers disclosed in Patent Document 1 is used, the pulling property of the hair bundle may not be sufficiently good.SUMMARY

[0005] One or more embodiments of the present invention have been made in view of the above, and a polyacrylonitrile-based artificial hair fiber including a hair bundle of polyacrylonitrile-based artificial hair fibers having an excellent pulling property with water repellency maintained, and a hair ornament product including the fiber are provided.

[0006] The present inventors have found that the above can be addressed by allowing an oil agent including a specific water repellent, a specific modified silicone, and a specific antistatic agent to adhere to a polyacrylonitrile-based synthetic fiber and by intensively examining an adhesion amount of each component included in the oil agent, and have completed one or more embodiments of the present invention.

[0007] One or more embodiments of the present invention relate to the following polyacrylonitrile-based artificial hair fiber, and a hair ornament product including the fiber.

[0008] [1] A polyacrylonitrile-based artificial hair fiber including a polyacrylonitrile-based synthetic fiber (A),

[0009] an alkyl (meth)acrylate-based water repellent (B), modified silicone (C) having an amino group, and an ionic antistatic agent (D) adhering to the polyacrylonitrile-based synthetic fiber (A),

[0010] the alkyl (meth)acrylate-based water repellent (B) not having a fluoro group,

[0011] the alkyl (meth)acrylate-based water repellent (B) having a long-chain hydrocarbon side chain, and

[0012] a total adhesion amount of the alkyl (meth)acrylate-based water repellent (B), the modified silicone (C) having an amino group, and the ionic antistatic agent (D) being 0.1% omf or more and 0.4% omf or less with respect to an entire mass of the polyacrylonitrile-based synthetic fiber (A).

[0013] [2] The polyacrylonitrile-based artificial hair fiber as described in [1], in which a mass ratio of an adhesion amount of the alkyl (meth)acrylate-based water repellent (B) to an adhesion amount of the modified silicone (C) having an amino group satisfies (B):(C)=1:0.02 or more and 0.15 or less.

[0014] [3] The polyacrylonitrile-based artificial hair fiber as described in [1] or [2], in which a mass ratio of the adhesion amount of the alkyl (meth)acrylate-based water repellent (B) to an adhesion amount of the ionic antistatic agent (D) satisfies (B):(D)=1:0.15 or more and 0.40 or less.

[0015] [4] The polyacrylonitrile-based artificial hair fiber as described in any one of [1] to [3], in which the alkyl (meth)acrylate-based water repellent (B) further includes a constituent unit derived from vinyl chloride.

[0016] [5] The polyacrylonitrile-based artificial hair fiber as described in any one of [1] to [4], in which a cross-sectional shape in a direction perpendicular to a longitudinal direction of the fiber is one kind selected from the group consisting of a dumbbell shape, a round shape, a C-letter shape, and a Y-letter shape.

[0017] [6] The polyacrylonitrile-based artificial hair fiber as described in any one of [1] to [5], in which an average friction coefficient (MIU) of the fibers is 0.175 or more and 0.30 or less.

[0018] [7] The polyacrylonitrile-based artificial hair fiber as described in any one of [1] to [6], in which a single fiber fineness is 5 dtex or more and 100 dtex or less.

[0019] [8] A hair ornament product including the polyacrylonitrile-based artificial hair fiber as described in any one of [1] to [7].

[0020] [9] The hair ornament product as described in [8], in which the hair ornament product is at least one selected from the group consisting of a hair wig, a hairpiece, a weaving, a hair extension, a braid hair, a hair accessory, and a doll hair.

[0021] One or more embodiments of the present invention can provide a polyacrylonitrile-based artificial hair fiber including a hair bundle of polyacrylonitrile-based artificial hair fibers having an excellent pulling property with water repellency maintained, and a hair ornament product including the fiber.DETAILED DESCRIPTION<<Polyacrylonitrile-Based Artificial Hair Fiber>>

[0022] A polyacrylonitrile-based artificial hair fiber includes a polyacrylonitrile-based synthetic fiber (A).

[0023] In the polyacrylonitrile-based artificial hair fiber, an alkyl (meth)acrylate-based water repellent (B), a modified silicone (C) having an amino group, and an ionic antistatic agent (D) adhere to the polyacrylonitrile-based synthetic fiber (A).

[0024] The total adhesion amount of the alkyl (meth)acrylate-based water repellent (B), the modified silicone (C) having an amino group, and the ionic antistatic agent (D) is 0.1% omf or more and 0.4% omf or less with respect to the entire mass of the polyacrylonitrile-based synthetic fiber (A).

[0025] According to one or more embodiments of the present invention, since the total adhesion amount of the alkyl (meth)acrylate-based water repellent (B), the modified silicone (C) having an amino group, and the ionic antistatic agent (D) is in a specific range, a hair bundle of polyacrylonitrile-based artificial hair fibers has an excellent pulling property with water repellency maintained.

[0026] Hereinafter, essential or optional components included in the polyacrylonitrile-based artificial hair fiber will be described.(Polyacrylonitrile-Based Synthetic Fiber (A))

[0027] An acrylonitrile-based polymer constituting the polyacrylonitrile-based synthetic fiber (A) is not particularly limited as long as it includes 25% by mass or more of a constituent unit derived from acrylonitrile, and for example, an acrylonitrile-based polymer including 25% by mass to 100% by mass of a constituent unit derived from acrylonitrile and 0% by mass to 75% by mass of a constituent unit derived from other monomers can be used. The acrylonitrile-based polymer may include 95% by mass or less of the constituent unit derived from acrylonitrile and 5% by mass or more of the constituent unit derived from the other monomer, may include 908 by mass or less of the constituent unit derived from acrylonitrile and 10% by mass or more of the constituent unit derived from the other monomer, and may include 30% by mass to less than 85% by mass of the constituent unit derived from acrylonitrile and more than 15% by mass and 70% by mass or less of the constituent unit derived from the other monomer.

[0028] The other monomer is not particularly limited as long as it is copolymerizable with acrylonitrile, and examples thereof include unsaturated carboxylic acids such as acrylic acid and methacrylic acid and salts thereof, acrylic acid esters such as methyl acrylate, methacrylic acid esters such as methyl methacrylate, esters of unsaturated carboxylic acids such as glycidyl methacrylate, vinyl esters such as vinyl acetate and vinyl butyrate, halogen-containing monomers, and sulfonic acid group-containing monomers. These may be used alone or may be used in combination of two or more thereof.

[0029] The acrylonitrile-based polymer may include 30% by mass to 80% by mass of the constituent unit derived from acrylonitrile, 20% by mass to 70% by mass of a constituent unit derived from a halogen-containing monomer, and 0% by mass to 5% by mass of a constituent unit derived from a sulfonic acid group-containing monomer, from the viewpoint of heat resistance, flame resistance, and dyeability. The acrylonitrile-based polymer may include 35% by mass to 75% by mass of the constituent unit derived from acrylonitrile, 25% by mass to 65% by mass of the constituent unit derived from the halogen-containing monomer, and 0% by mass to 5% by mass of the constituent unit derived from the sulfonic acid group-containing monomer, and may include 35% by mass to 75% by mass of the constituent unit derived from acrylonitrile, 24.5% by mass to 64.5% by mass of the constituent unit derived from the halogen-containing monomer, and 0.5% by mass to 5% by mass of the constituent unit derived from the sulfonic acid group-containing monomer.

[0030] Examples of the halogen-containing monomer include halogen-containing vinyl monomers such as vinyl chloride and vinyl bromide, and halogen-containing vinylidene monomers such as vinylidene chloride and vinylidene bromide. The halogen-containing monomer may be used alone or may be used in combination of two or more thereof. The halogen-containing monomer may include one or more selected from the group consisting of vinyl chloride and vinylidene chloride, or vinyl chloride, from the viewpoint of a sense of touch.

[0031] The sulfonic acid group-containing monomer is not particularly limited, and examples thereof include allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, isoprenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, as well as metal salts such as sodium salts thereof, and amine salts thereof. The sulfonic acid group-containing monomer may be used alone or may be used in combination of two or more thereof.

[0032] A method for manufacturing the polyacrylonitrile-based synthetic fiber (A) is not particularly limited, and, for example, a wet spinning method can be used. The wet spinning method is a method including extruding a spinning raw solution made of the acrylonitrile-based polymer from a spinning nozzle into a coagulation bath and coagulating the spinning raw solution in the coagulation bath to form a yarn. Furthermore, the wet spinning method may include any one of a water washing step, a drying step, a stretching step, and a thermal relaxation step in addition to the coagulation step.

[0033] The polyacrylonitrile-based synthetic fiber (A) may be manufactured by the above-described method, or a commercially available polyacrylonitrile-based synthetic fiber may be obtained. Examples of commercially available polyacrylonitrile-based synthetic fiber (A) include, for example, “AFRELLE” and “SYC” manufactured by Kaneka Corporation, and the like.(Alkyl (Meth)Acrylate-Based Water Repellent (B))

[0034] The alkyl (meth)acrylate-based water repellent (B) can be used as a non-fluorine-based water repellent. Therefore, the alkyl (meth)acrylate-based water repellent (B) does not include a fluoro group.

[0035] The alkyl (meth)acrylate-based water repellent (B) is a polymer including an acrylic acid ester, and / or a methacrylic acid ester and a constituent unit derived from a monomer copolymerizable therewith. The alkyl (meth)acrylate-based water repellent (B) has a long-chain hydrocarbon side chain on a side chain of the constituent unit or separately from the constituent unit. The long-chain hydrocarbon side chain may be a linear alkyl group having 12 to 24 carbon atoms, or a linear alkyl group having 16 to 22 carbon atoms.

[0036] The alkyl (meth)acrylate-based water repellent (B) may include a constituent unit derived from other monomers. Examples of the other monomer include halogenated olefins such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, vinylidene bromide, and vinylidene iodide. Among these, those including a constituent unit derived from vinyl chloride are preferable.

[0037] Examples of commercially available alkyl (meth)acrylate-based water repellent (B) include, for example, “NEOSEED NR 7080” manufactured by Nicca Chemical Co., Ltd.

[0038] An adhesion amount of the alkyl (meth)acrylate-based water repellent (B) may be 0.03% by mass or more and 1.0% by mass or less, 0.05% by mass or more and 0.75% by mass or less, or 0.1% by mass or more and 0.6% by mass or less with respect to the entire mass of the polyacrylonitrile-based synthetic fiber (A) from the viewpoint that a hair bundle of polyacrylonitrile-based artificial hair fibers has an excellent pulling property with water repellency maintained.

[0039] Note here that in the present specification, “(meth)acrylate” means both “acrylate” and “methacrylate”, and “(meth)acrylic” means both “acrylic” and “methacrylic”.(Modified Silicone (C) Having Amino Group)

[0040] The modified silicone (C) having an amino group includes a silicone having an amino group in which any site of a polydialkylsiloxane skeleton, which may be a polydimethylsiloxane skeleton (hereinafter, also collectively referred to as “polysiloxane”), of the silicone is substituted, modified silicones obtained by modifying one terminal, both terminals, or a side chain of a linear or branched polysiloxane, and a crosslinking modified silicone obtained by crosslinking the above modified silicones. Hereinafter, the modified silicone (C) having an amino group may also be referred to as “amino-modified silicone (C)”.

[0041] Examples of commercially available amino-modified silicone (C) include, “POLON-MF-63” manufactured by Shin-Etsu Chemical Co., Ltd., and “DOWSILIMBY22-079” manufactured by Dow Toray Co., Ltd., “Marposil Coat FZ-1” manufactured by Matsumoto Yushi-Seiyaku Co., Ltd., and the like.

[0042] An adhesion amount of the amino-modified silicone (C) may be 0.002% by mass or more and 0.05% by mass or less, 0.002% by mass or more and 0.04% by mass or less, or 0.002% by mass or more and 0.03% by mass or less with respect to the entire mass of the polyacrylonitrile-based synthetic fiber (A), from the viewpoint that a hair bundle of polyacrylonitrile-based artificial hair fibers has an excellent pulling property with water repellency maintained.(Ionic Antistatic Agent (D))

[0043] Examples of the ionic antistatic agent (D) include anionic antistatic agents such as higher fatty acid salts, higher alcohol sulfate ester salts, sulfated oils, and sulfonates; cationic antistatic agents such as alkyl amine salts, quaternary ammonium salts, imidazolinium salts, and guanidine salts; and amphoteric antistatic agents such as amine oxide type and betaine type antistatic agents.

[0044] The ionic antistatic agent (D) may be used alone or may be used in combination of two or more thereof.

[0045] An adhesion amount of the ionic antistatic agent (D) may be 0.01% by mass or more and 0.4% by mass or less, or 0.01% by mass or more and 0.3% by mass or less with respect to the entire mass of the polyacrylonitrile-based synthetic fiber (A) from the viewpoint that a hair bundle of polyacrylonitrile-based artificial hair fibers has an excellent pulling property with water repellency maintained.

[0046] A total adhesion amount of the alkyl (meth)acrylate-based water repellent (B), the modified silicone (C) having an amino group, and the ionic antistatic agent (D) may be 0.1% omf or more and 0.4% omf or less, 0.1% omf or more and 0.35% omf or less, or 0.1% omf or more and 0.30% omf or less with respect to the entire mass of the polyacrylonitrile-based synthetic fiber (A) from the viewpoint that a hair bundle of polyacrylonitrile-based artificial hair fibers has an excellent pulling property with water repellency maintained.

[0047] The “% omf” means % by mass of the adhesion amount of adhering components with respect to the entire mass of the polyacrylonitrile-based synthetic fiber (A).

[0048] A mass ratio of the adhesion amount of the alkyl (meth)acrylate-based water repellent (B) to the adhesion amount of the modified silicone (C) having an amino group may satisfy (B):(C)=1:0.02 or more and 0.15 or less, (B):(C)=1:0.025 or more and 0.14 or less, or (B):(C)=1:0.025 or more and 0.13 or less from the viewpoint that a hair bundle of polyacrylonitrile-based artificial hair fibers has an excellent pulling property with water repellency maintained.

[0049] A mass ratio of the adhesion amount of the alkyl (meth)acrylate-based water repellent (B) to the adhesion amount of the ionic antistatic agent (D) may satisfy (B):(D)=1:0.15 or more and 0.40 or less, (B):(D)=1:0.18 or more and 0.35 or less, or (B):(D)=1:0.20 or more and 0.30 or less from the viewpoint that a hair bundle of polyacrylonitrile-based artificial hair fibers has an excellent pulling property with water repellency maintained.(Other Components)

[0050] The polyacrylonitrile-based artificial hair fiber may contain components other than the polyacrylonitrile-based synthetic fiber (A), an alkyl (meth)acrylate-based water repellent (B), amino-modified silicone (C), and an ionic antistatic agent (D) (hereinafter also referred to as “other components”) as long as the effect of one or more embodiments of the present invention are not impaired. Examples of the other components include a water-repellent aid; a gloss adjusting agent; a coloring agent such as an organic pigment, an inorganic pigment, and a dye; a light stabilizer; a thermal stabilizer; a fiber-sizing agent; a deodorant; a fragrance; an insect repellent; an antibacterial agent; a crosslinking agent, and the like.(Water-Repellent Aid (E))

[0051] The water-repellent aid (E) is a modified silicone having a non-polar substituent. The water-repellent aid (E) is not particularly limited, and examples thereof include an alkyl-modified silicone, an aryl-modified silicone, and an aralkyl-modified silicone. An alkyl group of the alkyl-modified silicone may be, for example, an alkyl group having 8 or more and 24 or less carbon atoms, or an alkyl group having 12 or more and 22 or less carbon atoms. These may be used alone or in combination of two or more.

[0052] Among these, the alkyl-modified silicone is preferable from the viewpoint that water repellency of polyacrylonitrile-based artificial hair fibers is excellent in use in combination with the above-described alkyl (meth)acrylate-based water repellent (B).

[0053] Examples of commercially available alkyl-modified silicones include “X-52-8046” manufactured by Shin-Etsu Chemical Co., Ltd.

[0054] An adhesion amount of the water-repellent aid (E) can be appropriately selected within a range not impairing one or more embodiments of the present invention, and may be 0.003% by mass or more and 0.05% by mass or less, or 0.004% by mass or more and 0.04% by mass or less with respect to the entire mass of the polyacrylonitrile-based synthetic fiber (A).(Cross-Sectional Shape)

[0055] In the polyacrylonitrile-based artificial hair fiber, a cross-sectional shape in the direction perpendicular to the longitudinal direction of the fiber may be, for example, a round shape, an elliptic shape, a star shape, a dumbbell shape, a C-letter shape, a Y-letter shape, and any other shapes. Among these, from the viewpoint of ease in handling and braiding of hair when braiding as a hair ornament product, a dumbbell shape, a round shape, a C-letter shape, and a Y-letter shape are preferable, a dumbbell shape or a round shape is more preferable, and a dumbbell shape is particularly preferable.(Single Fiber Fineness)

[0056] The single fiber fineness of the polyacrylonitrile-based artificial hair fiber is not particularly limited, and may be, for example, 5 dtex or more and 100 dtex or less, and from the viewpoint of suitable use as artificial hair, the single fiber fineness may be 10 dtex or more and 90 dtex or less, 20 dtex or more and 80 dtex or less, 30 dtex or more and 70 dtex or less, or 35 dtex or more and 65 dtex or less.(Average Friction Coefficient of Hair Bundle)

[0057] An average friction coefficient (MIU) of fibers of a hair bundle of polyacrylonitrile-based artificial hair fibers may be 0.175 or more and 0.30 or less, 0.180 or more and 0.30 or less, or 0.185 or more and 0.30 or less, from the viewpoint that the hair bundle is excellent in the pulling property.

[0058] The average friction coefficient is measured using a friction test apparatus (KES-SE Friction Tester manufactured by KATO TECH CO., LTD.) using a sample obtained by forming a hair bundle of polyacrylonitrile-based artificial hair fibers of, for example, 10 cm to 40 cm and 0.5 g to 10 g, fixing one end of the hair bundle with a binder such as a binding band, and combing the hair bundle with a comb.

[0059] In general, the larger the value of the average friction coefficient, the rougher the surface of fibers, and the smaller the value, the smoother the surface of fibers.(Pulling Property of Hair Bundle)

[0060] The pulling property hair bundle of the of the polyacrylonitrile-based artificial hair fibers is evaluated as follows. The hair bundle of the fibers with a total fiber fineness of 1.2 million to 1.3 million dtex packed in a corrugated cardboard box are pulled out from the bottom of the box, hooked to parallel bars at 3 m height, and 20 m of the hair bundle is pulled out at a speed of 3 m / min. A displacement in the fiber direction from the box to the parallel bars at this point is evaluated. The displacement in the fiber direction of the hair bundle may be 5 cm or more and less than 10 cm, or 0 cm or more and less than 5 cm.(Water Repellency of Hair Bundle)

[0061] The water repellency of a hair bundle of polyacrylonitrile-based artificial hair fibers is evaluated by the water absorption rate of the hair bundle when the hair bundle is immersed in water at 90° C. for 15 seconds.

[0062] The water absorption rate of the polyacrylonitrile-based artificial hair fiber may be 20% or less, 10% or less, or 8% or less from the viewpoint of maintaining the water repellency.(Application of Use)

[0063] A hair bundle of the polyacrylonitrile-based artificial hair fibers is excellent in pulling property while the water repellency is maintained as described above. Therefore, the polyacrylonitrile-based artificial hair fiber and the hair bundle thereof can be suitably used for hair ornament products.<<Method for Manufacturing Polyacrylonitrile-Based Artificial Hair Fiber>>

[0064] One or more embodiments of the method for manufacturing the polyacrylonitrile-based artificial hair fiber include obtaining a coagulated yarn by wet spinning a spinning solution including an acrylonitrile-based polymer, and bringing the yarn to be treated before drying into contact with an oil agent including the alkyl (meth)acrylate-based water repellent (B), the amino-modified silicone (C), and the ionic antistatic agent (D).

[0065] According to the manufacturing method of one or more embodiments, as described above, polyacrylonitrile-based artificial hair fiber having excellent pulling property with the water repellency maintained can be manufactured.

[0066] Hereinafter, a step of obtaining a coagulated yarn by wet spinning a spinning solution including an acrylonitrile-based polymer (hereinafter, also referred to as “coagulation step”), a step of bringing the yarn to be treated before drying into contact with an oil agent including the alkyl (meth)acrylate-based water repellent (B), the amino-modified silicone (C), and the ionic antistatic agent (D) (hereinafter, also referred to as “contact step”), and optional steps are described.<Coagulation Step>(Acrylonitrile-Based Polymer)

[0067] The acrylonitrile-based polymer is a raw material for manufacturing a yarn of the polyacrylonitrile-based synthetic fiber (A). The acrylonitrile-based polymer is the same as that of one or more embodiments of the acrylonitrile-based polymer described in the item “Polyacrylonitrile-based synthetic fiber (A)”.(Spinning Solution)

[0068] The spinning solution contains the acrylonitrile-based polymer and an organic solvent. The organic solvent is not particularly limited, and it is preferable to use a good solvent for the acrylonitrile-based polymer. Examples of the good solvent for the acrylonitrile-based polymer include dimethyl sulfoxide (DMSO), N, N-dimethylacetamide (DMAC), N, N-dimethylformamide (DMF), acetone, and the like. Among these, acetone may be used from the viewpoint of versatility. Furthermore, dimethyl sulfoxide may be used from the viewpoint of high safety. The spinning solution may include a small amount of water, for example, 1.5% by mass or more and 4.8% by mass or less of water. This can suppress formation of voids.(Other Additives)

[0069] The spinning solution may include other additives for improving fiber characteristics, if necessary, within a range that does not impair the effect of one or more embodiments of the present invention. Examples of the other additives include a gloss adjusting agent, a coloring agent such as an organic pigment, an inorganic pigment, and a dye, and a stabilizer for improving light resistance or heat resistance.(Coagulation Step)

[0070] The coagulation step is a step of discharging the spinning solution through a spinning nozzle into a coagulation solution (coagulation bath) and coagulating the solution to form a yarn (hereinafter, such a yarn is also referred to as a “coagulated yarn”). An operation of the coagulation step is not particularly limited, and may be, for example, a wet spinning method of directly discharging a spinning solution in a raw solution tank into a coagulation solution according to a routine procedure. Furthermore, the operation may be a dry-wet spinning method of once discharging a spinning solution into the air from the spinning nozzle and then introducing it into the coagulation solution.

[0071] A temperature of the spinning solution is not particularly limited as long as it is a temperature at which the spinning solution can be stably maintained without being changed over time in the raw solution tank, and the temperature may usually be, for example, 40° C. or more and 70° C. or less.

[0072] A composition of the coagulation solution is not particularly limited, and, for example, an aqueous solution of a good solvent such as acetone may be used. A concentration of the good solvent is not particularly limited, and may be, for example, 10% by mass or more and 70% by mass or less. When the concentration is less than 10% by mass, coagulation becomes rapid, a coagulation structure becomes coarse, and voids tend to be formed inside the fibers.

[0073] A temperature of the coagulation solution is not particularly limited, and may be, for example, 5° C. or higher and 40° C. or lower.

[0074] The spinning nozzle can be appropriately used in accordance with an intended fiber cross section. The fiber cross section is not particularly limited, and may be any cross section such as a round shape, an elliptical shape, and irregular shapes.

[0075] An amount of the spinning solution discharged from the spinning nozzle is not particularly limited, and may be, for example, 0.1 g / min or more as a single-hole discharge amount. A spinning speed of the spinning solution from the spinning nozzle is not particularly limited, and may be 2 m / min or more and 17 m / min or less from the viewpoint of industrial productivity.

[0076] The coagulated yarn (fiber) that has passed through the coagulation solution is wound up by, for example, a winding roller via a feed roller, according to a routine procedure, and, as a result, an unstretched yarn is obtained. Furthermore, the coagulated yarn (fiber) may continuously proceed to other steps without being wound up.(Other Steps)

[0077] The wet spinning may include steps other than the coagulation step (hereinafter, also referred to as “other steps”) as long as the effect of one or more embodiments of the present invention is not impaired. Examples of the other steps include a water washing step, a drying step, a stretching step, and a thermal relaxation treatment step.

[0078] Examples of the stretching step include a wet stretching step carried out before the water washing step or after the water washing step and before the drying step, and a dry stretching step carried out after the drying step.

[0079] An order of each step is not particularly limited, and examples thereof include a method of carrying out a wet stretching step, a water washing step, a drying step, a dry stretching step, and a thermal relaxation treatment step sequentially after the coagulation step, or a method of carrying out a water washing step, a wet stretching step, a drying step, a dry stretching step, and a thermal relaxation treatment step sequentially after the coagulation step.(Wet Stretching Step)

[0080] The wet stretching step is a step of stretching a coagulated yarn in a stretching bath (hereinafter, also referred to as “primary stretching”). For the stretching bath, it is preferable to use an aqueous having solution a lower concentration of a good solvent such as acetone than the coagulation bath. A temperature of the stretching bath may be 30° C. or higher, or 40° C. or higher. A stretching ratio is not particularly limited, and may be 1.5 times or more and 8 times or less from the viewpoint of improving strength and productivity of the fibers. Note here that when the primary stretching is carried out using a water bath, the wet stretching step may be carried out after the water washing step to be described later, or the primary stretching and the water washing may be carried out simultaneously.(Water Washing Step)

[0081] The water washing step is a step of removing a good solvent such as acetone adhering to the yarn which has been subjected to the coagulation step or the wet stretching step. In the water washing step, from the viewpoint of easily removing the good solvent, for example, hot water of 70° C. or higher may be used.(Drying Step)

[0082] The drying step is a step of densifying the yarn by drying the yarn. A drying temperature is not particularly limited, and may be, for example, 110° C. or higher and 190° C. or lower.(Dry Stretching Step)

[0083] The dry stretching step is a step of stretching a yarn under heating conditions (hereinafter, also referred to as “secondary stretching”). A stretching temperature is not particularly limited, and may be, for example, 110° C. or higher and 190° C. or lower. A stretching ratio is not particularly limited, and may be, for example, 1 time or more and 4 times or less, 1.5 times or more and 3.5 times or less, or 1.5 times or more and 3 times or less.

[0084] Note here that an entire stretching ratio including wet stretching before drying may be 2 times or more and 10 times or less, 2 times or more and 8 times or less, 2 times or more and 6 times or less, or 2 times or more and 4 times or less.(Thermal Relaxation Treatment Step)

[0085] The thermal relaxation treatment step is a step of relaxing the yarn after being dry-stretched in a high temperature atmosphere. A relaxation rate is not particularly limited, and may be, for example, 5% or more, or 8% or more and 20% or less. The thermal relaxation treatment can be carried out, for example, in a dry heat atmosphere of 140° C. or higher and 200° C. or lower or in a superheated steam atmosphere.<Contact Step>(Yarn to be Treated Before Drying)

[0086] The yarn to be treated before drying is a yarn that is not dried and therefore is not densified, and is a yarn to be brought into contact with an oil agent described later. The yarn to be treated includes, in addition to the coagulated yarn obtained by the wet spinning, also yarns subjected to treatments other than the drying step, the dry stretching step, and the thermal relaxation treatment step described above. Specifically, the yarns to be treated include the coagulated yarn obtained by the wet spinning, a yarn after wet-stretching, and a yarn after washing with water. Among these, the yarn after washing with water is preferable from the viewpoint of preventing an organic solvent from being mixed into the oil agent.(Oil Agent)

[0087] The oil agent includes the above-described alkyl (meth)acrylate-based water repellent (B), amino-modified silicone (C), and an ionic antistatic agent (D). The oil agent may be used as a mixed solution in which the alkyl (meth)acrylate-based water repellent (B) or the like is dispersed or dissolved in water.

[0088] The oil agent may contain components other than the alkyl (meth)acrylate-based water repellent (B), the amino-modified silicone (C), the ionic antistatic agent (D), and water (hereinafter, also referred to as “other components”) as long as the effect of one or more embodiments of the present invention is not impaired. Examples of the other components include a water-repellent aid; a gloss adjusting agent; a coloring agent such as an organic pigment, an inorganic pigment, and a dye; a light stabilizer; a thermal stabilizer; a fiber-sizing agent; a deodorant; a fragrance; an insect repellent; an antibacterial agent; and a crosslinking agent.

[0089] Among these, the water-repellent aid is the same as that in the items of “(Water-repellent aid (E))”.(Contact Method)

[0090] A method for bringing a yarn to be treated into contact with an oil agent is not particularly limited, and examples of the method include an immersion method, a spraying method with a spray, a scattering method with a shower, and an applying method. Among these, the immersion method is preferable from the viewpoint of uniform contact of each component included in the oil agent.

[0091] A contact temperature is not particularly limited, and can be appropriately adjusted to 40° C. or higher and 90° C. or lower depending on a state of the yarn to be treated or an intended adhesion amount.

[0092] Also, contact time is not particularly limited, and can be appropriately adjusted to 1 second or longer and 10 minutes or shorter depending on the state of the yarn to be treated or the intended adhesion amount.

[0093] In one or more embodiments, it is preferable to dry the yarn after the contact treatment and then dry-stretch. By carrying out such a step, it is possible to manufacture a water-repellent polyacrylonitrile-based artificial hair fiber having excellent water repellency and also having an excellent sense of touch.<<Hair Ornament Product>>

[0094] A hair ornament product includes the above-described polyacrylonitrile-based artificial hair fiber.

[0095] The hair ornament product is not particularly limited, and, for example, may be at least one selected from the group consisting of a hair wig, a hairpiece, a weaving, a hair extension, a braid hair, a hair accessory, and a doll hair.

[0096] The polyacrylonitrile-based artificial hair fiber may be used alone as artificial hair to constitute a hair ornament product. Alternatively, in addition to the polyacrylonitrile-based artificial hair fiber, other artificial hair fibers and natural fibers such as human hair and animal hair may be combined to constitute a hair ornament product. The other artificial hair fibers are not particularly limited, and examples thereof include polyvinyl chloride-based fibers, nylon fibers, polyester fibers, regenerated collagen fibers, and the like.EXAMPLES

[0097] Hereinafter, one or more embodiments of the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.Examples 1 to 8 and Comparative Examples 1 to 11<Production of Oil Agent>

[0098] The following water repellent (B), the following modified silicone (C), the following antistatic agent (D), the following water-repellent aid (E), and water were mixed in the contents described in the following Table 1 to prepare oil agents 1 to 8 and comparative oil agents 1 to 4, as oil agent aqueous solutions.

[0099] As the water repellent (B), the following B1 was used. B1: alkyl acrylate-based water repellent (“NEOSEED NR-7080”, manufactured by Nicca Chemical Co., Ltd.).

[0100] As the modified silicone (C), the following C1 to C2 were used.

[0101] C1: amino-modified silicone (“POLON-MF-63”, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0102] C2: epoxy-modified silicone (“MSW-2”, manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.)

[0103] As the ionic antistatic agent (D), the following D1 was used.

[0104] D1: quaternary ammonium salt

[0105] As the water-repellent aid (E), the following E1 was used.

[0106] E1: alkyl-modified siliconeTABLE 1Water-WaterModifiedAntistaticrepellentrepellent(B)silicone(C)agent(D)aid(E)Types / Types / Types / Types / Water% by% by% by% by% byRatiomassmassmassmassmass(B)(C)(D)(E)Oil agent 1B1 / 0.88C1 / 0.044D1 / 0.23E1 / 0.07498.771.000.050.260.084Oil agent 2B1 / 0.48C1 / 0.024D1 / 0.12E1 / 0.04199.331.000.050.260.084Oil agent 3B1 / 1.45C1 / 0.073D1 / 0.38E1 / 0.1297.971.000.050.260.084Oil agent 4B1 / 0.88C1 / 0.088D1 / 0.23E1 / 0.07498.731.000.100.260.084Oil agent 5B1 / 0.88C1 / 0.022D1 / 0.23E1 / 0.07498.791.000.0250.260.084ComparativeB1 / 0.88C2 / 0.044D1 / 0.23E1 / 0.07498.771.000.050.260.084oil agent 1ComparativeB1 / 1.30C2 / 0.65D1 / 0.65E1 / 0.1197.291.000.500.500.084oil agent 2ComparativeB1 / 0.88C2 / 0.044D1 / 0.40E1 / 0.07498.601.000.050.450.084oil agent 3ComparativeB1 / 1.06C2 / 0.053D1 / 0.28E1 / 0.09098.521.000.050.260.084oil agent 4<Examples of Fiber Manufacture>Examples 1 to 5 and Comparative Examples 1 to 4

[0107] An acrylonitrile-based polymer obtained by copolymerizing 49% by mass of acrylonitrile, 50.5% by mass of vinyl chloride, and 0.5% by mass of sodium styrene sulfonate was dissolved in acetone to produce a resin solution having a resin concentration of 29.5% by mass. Next, a black pigment (acetone solution, 10.5% by mass) as a coloring agent was added to the resin solution in a concentration of 19.2% by mass with respect to 100% by mass of the acrylonitrile-based polymer to produce a spinning raw solution. Into a coagulation bath of an acetone aqueous solution of 25° C. and 25% by mass, the spinning raw solutionwas extruded using a spinning nozzle (hole diameter: 0.4 mm, number of holes: 100, dumbbell-shape) and wet-spun at a spinning speed of 5 m / min, and then stretched 2.0 times in a stretching bath of an acetone aqueous solution of 50° C. and 20% by mass to obtain the polyacrylonitrile-based synthetic fiber (A). Subsequently, a yarn was subjected to water washing with hot water at 80° C. while being stretched 1.1 times, immersed for 1 to 2 seconds in an oil agent tank (60° C.) into which each oil agent described in Table 1 had been introduced to allow the yarn to be immersed in the oil agent, and then the oil agent was squeezed by a nip roll so that 20% by mass adhered to 100% by mass of the polyacrylonitrile-based synthetic fiber (A). Subsequently, the yarn was dried at 130° C., then stretched 2.1 times, and subjected to 8% relaxation shrinkage under heat treatment conditions at 150° C. for 90 seconds to produce polyacrylonitrile-based artificial hair fibers having a single fiber fineness of about 46 dtex of Examples 1 to 5 and Comparative Examples 1 to 4 described in the following Table 2.Example 6 and Comparative Example 7 to 8

[0108] An acrylonitrile-based polymer obtained by copolymerizing 49% by mass of acrylonitrile, 50.5% by mass of vinyl chloride, and 0.5% by mass of styrene sulfonate was dissolved in acetone to produce a resin solution having a resin concentration of 29.5% by mass. Next, a black pigment (acetone solution, 10.5% by mass) as a coloring agent was added to the resin solution in a concentration of 19.2% by mass with respect to 100% by mass of the acrylonitrile-based polymer to produce a spinning raw solution. The spinning raw solution was extruded using a spinning nozzle (hole diameter: 0.36 mm, number of holes: 100, C type) into a coagulation bath of an acetone aqueous solution of 25° C. and 25% by mass and wet-spun at a spinning speed of 5 m / min, and then stretched 2.0 times in a stretching bath of 20% by mass of an acetone aqueous solution at 50° C. to obtain the polyacrylonitrile-based synthetic fiber (A). Subsequently, a yarn was subjected to water washing with hot water at 80° C. while being stretched 1.1 times, immersed for 1 to 2 seconds in an oil agent tank (60° C.) into which each oil agent described in Table 1 had been introduced, and immersed in the oil agent, and then the oil agent was squeezed by a nip roll so that the oil agent at the solution content rate shown in Table 2 adhered to 100% by mass of the polyacrylonitrile-based synthetic fiber (A). Subsequently, the yarn was dried at 130° C., then stretched 2.1 times, and subjected to 8% relaxation shrinkage under heat treatment conditions at 150° C. for 90 seconds to produce polyacrylonitrile-based artificial hair fibers having a single fiber fineness of about 51 dtex of Example 6 and Comparative Examples 7 to 8 described in the following Table 2.Example 7 and Comparative Example 9 to 10

[0109] Acrylic-based artificial hair fibers of Example 7 and Comparative Examples 9 to 10 described in the following Table 2 having a single fiber fineness of about 51 dtex were obtained in the same manner as in Example 6 except that a spinning nozzle (hole diameter: 0.38 mm, number of holes: 100, Y-shape) was used.Example 8 and Comparative Example 11

[0110] Acrylic-based artificial hair fibers having a single fiber fineness of about 36 dtex of Example 8 and Comparative Example 11 described in the following Table 2 were obtained in the same manner as in Example 6 except that a spinning nozzle (hole diameter: 0.27 mm, number of holes: 100, round shape) was used.Comparative Examples 5 to 6

[0111] Acrylic-based artificial hair fibers having a single fiber fineness of about 46 dtex of Comparative Examples 5 to 6 described in the following Table 2 were obtained in the same manner as in Example 6 except that a spinning nozzle (hole diameter: 0.40 mm, number of holes: 100, dumbbell-shape) was used.TABLE 2Water repellencyAdhesion amount of oil agent (% omf)F / FCross-Water(B) +Solutionfrictionsectionalabsorption(C) +contentcoefficientPullingshaperateEvaluation(B)(C)(D)(E)(D)rate (%)MIUpropertyExample 1Oil agent 1Dumbbell5.4%◯0.1430.0070.0370.0120.188200.188⊚shapeExample 2Oil agent 2Dumbbell9.3%◯0.1430.0070.0370.0120.188200.237⊚shapeExample 3Oil agent 3Dumbbell18.5%Δ0.1080.0050.0280.0090.141200.192⊚shapeExample 4Oil agent 4Dumbbell7.1%◯0.2150.0110.0560.0180.282200.188⊚shapeExample 5Oil agent 5Dumbbell7.8%◯0.1390.0140.0360.0120.188200.216◯shapeComparativeComparativeDumbbell6.7%◯0.1910.0100.0500.0160.250200.170XExample 1oil agent 1shapeComparativeComparativeDumbbell30.0%X0.2600.1300.1300.0220.520200.170ΔExample 2oil agent 2shapeComparativeComparativeDumbbell17.8%Δ0.1600.0080.0720.0140.240200.156XExample 3oil agent 3shapeComparativeComparativeDumbbell34.8%X0.4120.0210.1070.0350.540200.139ΔExample 4oil agent 4shapeExample 6Oil agent 1C14.4%◯0.1010.0050.0260.0080.132390.272◯Example 7Oil agent 1Y19.2%Δ0.2510.0130.0650.0210.329870.199⊚Example 8Oil agent 1Round9.2%◯0.1430.0070.0370.0120.188500.220⊚shapeComparativeOil agent 1Dumbbell10.7%◯0.0650.0030.0170.0050.085230.277ΔExample 5shapeComparativeOil agent 1Dumbbell40.0%X0.3230.0160.0840.0270.4231120.190⊚Example 6shapeComparativeOil agent 1C13.5%◯0.0360.0020.0090.0030.047120.292ΔExample 7ComparativeOil agent 1C35.0%X0.3230.0160.0840.0270.4231120.256⊚Example 8ComparativeOil agent 1Y18.5%Δ0.0360.0020.0090.0030.047120.213ΔExample 9ComparativeOil agent 1Y35.7%X0.3230.0160.0840.0270.4231120.185⊚Example 10ComparativeOil agent 1Round30.5%X0.3230.0160.0840.0270.4231120.190⊚Example 11shape

[0112] In Table 2, the adhesion amounts “% omf” of the water repellent (B), the modified silicone (C), the ionic antistatic agent (D), and the water-repellent aid (E) represent % by mass of the water repellent (B), the modified silicone (C), the ionic antistatic agent (D), and the water-repellent aid (E) with respect to an entire mass of the polyacrylonitrile-based synthetic fiber (A). Note here that each of the adhesion amounts of the water repellent (B), the modified silicone (C), the ionic antistatic agent (D), and the water-repellent aid (E) was calculated by producing the polyacrylonitrile-based artificial hair fiber, then extracting an oil agent in a state where each component is mixed from the fiber, and calculating the adhesion amount of each component using a mixing ratio from the extraction amount.<Evaluation>

[0113] The obtained hair bundle of polyacrylonitrile-based artificial hair fibers was evaluated for the water repellency, average friction coefficient, and pulling property according to the following method. Results are shown in Table 2.(Water Repellency:Water Absorption Rate)

[0114] A hair bundle with a total fiber fineness of 1,242,000 dtex was formed and cut into 10 cm pieces, and a portion at 1 cm from one end of each piece was fixed with a binding band. Next, distilled water was added to a water bath up to a portion 1 cm below an edge thereof, and a mass of the hair bundle cut into 10 cm pieces, which was warmed to 90° C. was measured. The hair bundle was immersed in water at 90° C. for 15 sec, and then taken out from the water bath and left in the air for 15 sec. A weight of the hair bundle after immersion with water was measured, and then, the water absorption rate of the hair bundle was measured from the following calculation formula, and evaluated as follows.(Weight⁢ of⁢ hair⁢ bundle⁢ after⁢ being⁢ immersedin⁢ water-Weight⁢ of⁢ binding⁢ bandWeight⁢ of⁢ hair⁢ bundle⁢ before⁢ being⁢ immersedin⁢ water-Weight⁢ of⁢ binding⁢ band-1)×100[Math. 1]0 to 15%: high water repellency is observed (o: circle symbol) 15 to 30%: water repellency is observed (Δ: triangle symbol) 30% or more: sufficient water repellency is not observed (x: cross symbol)(Average Friction Coefficient)A hair bundle of 30 cm and 4 g and a hair bundle of 12 cm and 0.8 g were formed, and a portion of 1 cm from one end of each bundle was fixed with a binding band, and the hair bundles were combed with a comb about twice to prevent tangling. Then, the hair bundles were respectively set to a sample stage and a friction element of the friction test apparatus (KES-SE Friction Tester manufactured by KATO TECH CO., LTD.), and subjected to measurement. The measurement was carried out twice, and an average value of the two readings of the average friction coefficient (MIU) was taken as the F / F friction coefficient (MIU).(Pulling Property)

[0116] The hair bundle with a total fiber fineness of 1.2 million to 1.3 million dtex packed in a corrugated cardboard box are pulled out from the bottom of the box, hooked to parallel bars at 3 m height, and 20 m of the hair bundle was pulled out at a speed of 3 m / min. Then, the displacement in the fiber direction of the hair bundle from the box to the parallel bars immediately after 20 m was pulled out was observed and evaluated in the following three levels.

[0117] ⊙ (bullseye symbol) (Very good): Displacement of the hair bundle in the fiber direction is 0 cm or more and less than 5 cm.

[0118] (Good): Displacement of the hair bundle in the fiber direction is 5 cm or more and less than 10 cm.

[0119] Δ (Poor): Displacement of the hair bundle in the fiber direction is 10 cm or more and less than 20 cm.

[0120] x (Very poor): Displacement of the hair bundle in the fiber direction is 20 cm or more.

[0121] From Table 2, it is shown that when the total adhesion amount of the alkyl (meth)acrylate-based water repellent (B), the modified silicone (C) having an amino group, and the ionic antistatic agent (D) is 0.1% omf or more and 0.4% omf or less, the pulling property and the water repellency of the hair bundle is excellent.

[0122] Although the disclosure has been described with respect to only a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that various other embodiments may be devised without departing from the scope of the present disclosure. Accordingly, the scope of the invention should be limited only by the attached claims.

Claims

1. A polyacrylonitrile-based artificial hair fiber comprising:a polyacrylonitrile-based synthetic fiber (A); andan alkyl (meth)acrylate-based water repellent (B), a modified silicone (C) having an amino group, and an ionic antistatic agent (D) adhering to the polyacrylonitrile-based synthetic fiber (A),wherein the alkyl (meth)acrylate-based water repellent (B) does not have a fluoro group,the alkyl (meth)acrylate-based water repellent (B) has a long-chain hydrocarbon side chain, anda total adhesion amount of the alkyl (meth)acrylate-based water repellent (B), the modified silicone (C) having an amino group, and the ionic antistatic agent (D) is 0.1% omf or more and 0.4% omf or less with respect to an entire mass of the polyacrylonitrile-based synthetic fiber (A).

2. The polyacrylonitrile-based artificial hair fiber according to claim 1, wherein a mass ratio of an adhesion amount of the alkyl (meth)acrylate-based water repellent (B) to an adhesion amount of the modified silicone (C) having an amino group satisfies (B):(C) of 1:0.02 to 1:0.15.

3. The polyacrylonitrile-based artificial hair fiber according to claim 1, wherein a mass ratio of an adhesion amount of the alkyl (meth)acrylate-based water repellent (B) to an adhesion amount of the ionic antistatic agent (D) satisfies (B):(D) of 1:0.15 to 1:0.40.

4. The polyacrylonitrile-based artificial hair fiber according to claim 1, wherein the alkyl (meth)acrylate-based water repellent (B) further comprises a constituent unit derived from vinyl chloride.

5. The polyacrylonitrile-based artificial hair fiber according to claim 1, wherein a cross-sectional shape in a direction perpendicular to a longitudinal direction of the polyacrylonitrile-based artificial hair fiber is one kind of shape selected from the group consisting of a dumbbell shape, a round shape, a C-letter shape, and a Y-letter shape.

6. The polyacrylonitrile-based artificial hair fiber according to claim 1, wherein an average friction coefficient (MIU) of fibers is 0.175 or more and 0.30 or less.

7. The polyacrylonitrile-based artificial hair fiber according to claim 1, wherein a single fiber fineness is 5 dtex or more and 100 dtex or less.

8. A hair ornament product comprising the polyacrylonitrile-based artificial hair fiber according to claim 1.

9. The hair ornament product according to claim 8, wherein the hair ornament product is at least one selected from the group consisting of a hair wig, a hairpiece, a weaving, a hair extension, a braid hair, a hair accessory, and a doll hair.

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