JP2009138314A - Artificial hair fiber, artificial hair, and hair accessory product composed of the artificial hair - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide polyester-based artificial hair having glossiness similar to that of human hair, and hair texture similar to that of natural human hair (moist feeling), and antibacterial property, and excellent in curl-keeping property, and to provide a hair accessory product comprising the artificial hair. <P>SOLUTION: The artificial hair having glossiness similar to that of human hair, hair texture similar to that of natural human hair (moist feeling), and antibacterial property, and excellent in curl-keeping property, is produced by weaving a composition containing 5-80 pts.mass of organic resin grains each having an average first granular diameter of 0.01-10 μm based on 100 pts.mass of a thermoplastic resin. The hair accessory product is composed of the artificial hair. The artificial hair is suitable to be processed into the hair accessory product such as a hair wig, a toupee, a weaving, a hair extension, a braid, a hair accessory, or doll hair. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to artificial hair and a hair ornament product comprising the same. More specifically, the present invention relates to artificial hair made of synthetic fibers, which suppresses gloss, which is a defect, and has a hair texture similar to human hair, so-called moist feeling, weaving and wig. In particular, the present invention relates to artificial hair suitably used as a head ornament product such as a two-piece hair extension or a hair accessory and a head ornament product comprising the same.

  In hair products such as wigs, hair wigs, furs, hair bands, doll hairs, human hair and artificial hair (modaacrylic fibers, polyvinyl chloride fibers) and the like are conventionally used. However, in recent years, it has become increasingly difficult to obtain human hair, and instead, artificial hair has become more important. As an artificial hair material, modacrylic fiber has been frequently used taking advantage of flame retardancy, but it was insufficient in terms of heat-resistant temperature. In recent years, artificial hair fibers using polyester fibers mainly composed of polyester typified by polyethylene terephthalate having excellent heat resistance have been proposed. However, the polyester fiber has a strong gloss as it is, and has a hard and squeezed (waxy) texture, which is a problem when used as an artificial hair material. For this reason, methods for improving these gloss and texture have been proposed. Usually, roughening the fiber surface is considered as a means of improving gloss and changing the texture. Fine particles, such as titanium oxide, are used to deluster, but with this method, color is developed simply by delustering. It is well known that sex is worse. In addition, a technique has been proposed in which polyester fibers containing inorganic fine particles are alkali-etched to form specific irregularities on the fiber surface (Patent Document 1). This method is a technique for imparting an excellent darkening effect to the rough surface, but the difficulty is that the gloss is reduced and it is difficult to obtain a glossy dark effect.

Furthermore, although a method of mixing fine particles into a polymer matrix has been proposed (Patent Document 2), aggregation of particles in the polymer, increase in viscosity of the polymer melt or solution, decomposition of the fine particles themselves and the polymer in the production process, There are drawbacks such as deterioration and deterioration of physical properties of the molded fiber.
Artificial hair made of polyester fiber is a so-called crisp hair that has been dried out of moisture and resin, so-called hair that feels moist and contains moderate moisture. The hair texture was poor, and a hair texture similar to natural human hair was not obtained.

As a method for adjusting the hair texture, for example, a technique for imparting a moist texture to the fiber by uniformly forming a weft on the surface of the polyester fiber is disclosed (Patent Document 3).
However, the actual condition is that polyester-based artificial hair having a glossy feeling close to that of human hair and having a hair texture similar to natural human hair (moist feeling) has not yet been obtained.
JP-A-55-107512 JP 2005-42234 A Japanese Patent Laid-Open No. 9-273026

  The present invention solves the conventional problems as described above, has a glossy feeling close to human hair, and a hair texture (moist feeling) similar to natural human hair, and has coloring (transparency) and combing properties. An object is to provide excellent artificial hair and a headdress product comprising the same.

  As a result of intensive studies to solve the above problems, the present inventors form fibers from a composition comprising organic resin particles having an average primary particle diameter of 0.01 μm to 10 μm in a thermoplastic resin. It is possible to obtain polyester artificial hair and hair ornament products made of it with glossiness close to human hair, hair texture similar to natural human hair (moist feeling), antibacterial properties, and excellent curl retention The headline and the present invention were completed.

  That is, the present invention is an artificial hair formed from a composition containing 100 parts by mass of a thermoplastic resin (A) and 5-80 parts by mass of organic resin particles (B) having an average primary particle size of 0.01 μm to 10 μm. It is related with the fiber for artificial and artificial hair.

  In a preferred embodiment, the thermoplastic resin (A) is one or more polymers selected from the group consisting of polyolefin resins, polyvinyl chloride resins, acrylic resins, polyester resins, and polyamide resins. It is a fiber for hair and artificial hair.

  In a more preferred embodiment, the artificial hair fiber and the artificial hair, in which the organic resin particles (B) are at least one organic resin selected from regenerated collagen, polyvinyl alcohol, and carboxymethylcellulose.

  In a more preferred embodiment, the organic resin particles (B) are artificial hair crosslinked with an aluminum salt, the organic resin particles (B) contain a crosslinking component, and the crosslinking component is represented by the general formula (1). A fiber for artificial hair that is a monofunctional epoxy compound, and artificial hair,

（但し、ＲはＲ^１−、Ｒ^２−Ｏ−ＣＨ_２−、またはＲ^２−ＣＯＯ−ＣＨ_２−で表される置換基を示し、Ｒ^１は炭素数２以上の炭化水素基またはＣＨ_２Ｃｌであり、Ｒ^２は炭素数４以上の炭化水素基。）
アルミニウム塩が次式で表される人工毛髪用繊維、及び人工毛髪である。

(However, R represents a substituent represented by R ¹ —, R ² —O—CH ₂ —, or R ² —COO—CH ₂ —, and R ¹ represents a hydrocarbon group having 2 or more carbon atoms or CH _2. Cl and R ² is a hydrocarbon group having 4 or more carbon atoms.)
The aluminum salt is a fiber for artificial hair represented by the following formula, and artificial hair.

Al (OH) _n Cl _3-n or Al ₂ (OH) _2n (SO ₄ ) _3-n
(However, n = 0.5 to 2.5)
Furthermore, the fiber for artificial hair and the artificial hair have a fiber surface roughness (ten-point average roughness) Rz of 0.50 to 1.50 μm.

  Furthermore, the artificial hair is processed and used as a head ornament product, specifically, a head ornament product such as a weaving, wig, two-piece, hair extension, or hair accessory. The head ornament product obtained by the present invention does not have a sense of incongruity due to the difference in glossiness with human hair even when used together with human hair, and has a moist feeling similar to natural human hair.

  According to the present invention, it is possible to obtain a polyester-based artificial hair having a glossiness close to human hair, a hair texture similar to natural human hair (moist feeling), antibacterial properties, and excellent curl retention, and a head decoration product comprising the same. be able to. And the hair ornament product obtained using the artificial hair of this invention does not have a sense of incongruity even if it uses it with human hair, and is preferably used as hair ornament products, such as a hair wig and a two-piece.

  The fiber for artificial hair and artificial hair of the present invention contain 100 parts by mass of the thermoplastic resin (A) and 5-80 parts by mass of organic resin particles (B) having an average primary particle size of 0.01 μm to 10 μm. It is a fiber for artificial hair formed from a product, and artificial hair.

  Here, the artificial hair of the present invention refers to artificial hair obtained using the artificial hair fiber of the present invention.

  In addition, in the following description, when all the characteristics of the fiber for artificial hair and the artificial hair are expressed, it has described as the artificial hair of the present invention.

  The thermoplastic resin (A) used in the present invention can be used regardless of crystalline or non-crystalline as long as it can be fiberized.

Examples of the thermoplastic resin (A) include polyolefin resins, polyvinyl chloride resins, acrylic resins, polyester resins, and polyamide resins. Specifically, for example, low density polyethylene, high density polyethylene, Polyolefins which are homopolymers of olefins such as polypropylene, poly-1-butene, poly-4-methyl-1-pentene,
Copolymerized polyolefins which are random or block copolymers of α-olefins such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, ethylene / acrylic acid copolymers, ethylene-vinyl acetate copolymers , Ethylene-vinyl alcohol copolymer, ethylene-vinyl compound copolymer such as ethylene-vinyl chloride copolymer, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-styrene copolymer Polymer, Styrene copolymer such as α-methyl styrene-styrene copolymer, Vinyl chloride, Polyvinylidene chloride, Vinyl chloride-vinylidene chloride copolymer, Vinyl acrylate, Polymethyl methacrylate, etc. Polymer, nylon 6, nylon 66 Polyamides such as nylon 610, nylon 612, nylon 11 and nylon 12, thermoplastic polyesters such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, polyarylate and polyphenylene oxide. These may be used alone or in combination of two or more. Among these, modacrylic, polyvinyl chloride, polyvinylidene chloride, polypropylene, nylon 6, nylon 66, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, copolymer polyester (ethylene terephthalate as the main component, ethylene glycol of bisphenol A) Preferred are polyesters copolymerized with ether, polyesters copolymerized with 1,4-cyclohexanedimethanol, polyesters copolymerized with 5-sodium sulfoisophthalate, and the like.
The organic resin particles (B) of the present invention are preferably at least one organic resin particle selected from regenerated collagen, polyvinyl alcohol and carboxymethylcellulose. In the present specification, the particles are also referred to as powder.
(1) Regenerated collagen particles The regenerated collagen particles of the present invention will be described below. The present invention has a conventional collagen powder by producing a solubilized collagen solution from the skin, bones, tendons, etc. of animals such as cows, pigs, horses, deer, rabbits, birds, fish, etc. It is possible to provide a novel collagen powder that can solve the quality problem. Furthermore, a solubilized collagen aqueous solution is spun into a regenerated collagen fiber, thereby providing a completely new collagen powder by thoroughly purifying the collagen and carrying out close crosslinking in the fiberizing process by spinning.

  As a method for producing the regenerated collagen, for example, as disclosed in Japanese Patent Application Laid-Open No. 2002-249882, it is preferable to use a part of the floor skin as a raw material. The floor skin is obtained from, for example, fresh floor skin obtained from animals such as cows, pigs, horses, deer, sea breams, birds, fish, and salted raw skin. Most of these skins are made of insoluble collagen fibers, and are usually used after removing the meaty portion adhering to the net and removing the salt used to prevent spoilage and alteration. In addition, other materials such as bones and tendons of the animals can be used in the same manner.

  The insoluble collagen fibers contain impurities such as lipids such as glyceride, phospholipids and free fatty acids, proteins other than collagen such as glycoproteins and albumin. These impurities have a great influence on quality such as gloss and strength, odor and the like when powdered. Therefore, for example, lime pickled to hydrolyze the fat in insoluble collagen fibers, unraveling the collagen fibers, and then subjected to leather treatments such as acid / alkali treatment, enzyme treatment, solvent treatment, etc. It is preferable to remove these impurities in advance.

  The insoluble collagen subjected to the treatment as described above is subjected to a solubilization treatment in order to cleave the cross-linked peptide portion. As the solubilization method, a publicly-known publicly known alkali solubilization method or enzyme solubilization method can be applied. When applying the alkali solubilization method, it is preferable to neutralize with an acid such as hydrochloric acid. In addition, you may use the method described in Japanese Patent Publication No.46-15033 as an improved method of the conventionally known alkali solubilization method.

  The enzyme solubilization method has an advantage that regenerated collagen having a uniform molecular weight can be obtained, and can be suitably employed in the present invention. As such an enzyme solubilization method, methods described in, for example, Japanese Patent Publication No. 43-25829 and Japanese Patent Publication No. 43-27513 can be employed. Further, the alkali solubilization method and the enzyme solubilization method may be used in combination.

  When the solubilized collagen is further subjected to operations such as pH adjustment, salting out, washing with water and solvent treatment, it is possible to obtain regenerated collagen with excellent quality and so on. It is preferable to apply a treatment. The solubilized collagen obtained has an acidity adjusted to pH 2 to 4.5 with an acid such as hydrochloric acid, acetic acid or lactic acid so as to be a stock solution having a predetermined concentration of, for example, 1 to 15% by mass, preferably about 2 to 10% by mass. Dissolved using solution. The obtained aqueous collagen solution may be defoamed with stirring under reduced pressure as necessary, and may be filtered to remove fine dust that is a water-insoluble matter. In the solubilized collagen aqueous solution obtained, if necessary, for example, a stabilizer for the purpose of improving mechanical strength, improving water resistance / heat resistance, improving gloss, improving spinnability, preventing coloring, preserving, etc. An appropriate amount of an additive such as a water-soluble polymer compound may be blended.

Regenerated collagen is formed by discharging the solubilized collagen aqueous solution through, for example, a spinning nozzle or a slit in the inorganic salt aqueous night. As the inorganic salt aqueous solution, for example, an aqueous solution of a water-soluble inorganic salt such as sodium sulfate, sodium chloride, or ammonium sulfate is used. Usually, the concentration of these inorganic salts is adjusted to 10 to 40% by mass. The pH of the inorganic salt aqueous solution is usually adjusted to pH 2 to 13, preferably pH 4 to 12, by adding a metal salt such as sodium borate or sodium acetate, hydrochloric acid, boric acid, acetic acid, sodium hydroxide, or the like. It is preferable. If pH is the said range, the peptide bond of collagen will be hard to receive a hydrolysis, and the target collagen powder will be obtained. Further, the temperature of the inorganic salt aqueous solution is not particularly limited, but it is usually preferably 35 ° C. or lower. If the temperature is below 35 ° C,
Soluble collagen does not denature, can maintain high strength, and can be manufactured stably. In addition, although the minimum of temperature is not specifically limited, Usually, it can adjust suitably according to the solubility of inorganic salt.

The free amino group of the collagen is modified with an alkyl group having 2 to 20 carbon atoms and having a hydroxyl group or an alkoxy group at the β-position or γ-position. The carbon number main chain indicates a continuous carbon chain of an alkyl group bonded to an amino group, and the number of carbons existing through other atoms is not considered. As a reaction for modifying a free amino group, a conventionally known alkylation reaction of an amino group can be used. The alkyl group having 2 to 20 carbon atoms having a hydroxyl group or an alkoxy group at the β-position is preferably a compound represented by the following general formula (2) in view of reactivity, ease of treatment after reaction, and the like.
—CH ₂ —CH (OX) —R (2)
In the formula, R represents a substituent represented by R ¹ —, R ² —O—CH ₂ — or R ² —COO—CH ₂ —, and R ¹ in the substituent is a hydrocarbon having 2 or more carbon atoms. Group or CH ₂ Cl, R ² represents a hydrocarbon group having 4 or more carbon atoms, and X represents hydrogen or a hydrocarbon group.

Preferable examples of the general formula (2) include a glycidyl group, a 1-chloro-2-hydroxypropyl group, and a 1,2-dihydroxypropyl group. In addition, a structure in which a glycidyl group is added to a free amino group in collagen can be mentioned. Furthermore, a structure in which the epoxy compound used is subjected to ring-opening addition and / or ring-opening polymerization starting from the hydroxyl group contained in the alkyl group described in the above-mentioned preferred group can be mentioned. Examples of the terminal structure include those having the aforementioned alkyl group structure.
Examples of amino acids constituting the free amino group of the regenerated collagen include lysine and hydroxylysine. Furthermore, although the amino acid that originally constitutes collagen is arginine, the amino group of ornithine, which is produced by partial hydrolysis during hydrolysis under alkaline conditions to obtain the regenerated collagen, is also present. Alkylation reaction is performed. In addition, the reaction proceeds with a secondary amine contained in histidine.

  The modification rate of the free amino group can be measured by amino acid analysis, and calculated based on the amino acid analysis value of the regenerated collagen fiber before the alkylation reaction or the known composition of the free amino acid constituting the collagen used as the raw material Is done. In the modification of the amino group in the present invention, the structure modified with an alkyl group having 2 or more carbon atoms having a hydroxyl group or an alkoxy group at the β 1-position or γ-position may be 50% or more of the free amino group. The other part may be a free amino group or a structure modified with another substituent. The modification rate of the free amino acid in the regenerated collagen needs to be 50% or more, more preferably 65% or more, and still more preferably 80% or more. When the reaction rate is low, good characteristics cannot be obtained due to heat resistance.

  Here, in the modification of the free amino group, one molecule of an alkylating agent usually reacts with respect to one free amino group. Of course, two or more molecules may react. Furthermore, an intramolecular or intermolecular cross-linking reaction may exist through a hydroxyl group, an alkoxy group or other functional group present at the β 1-position or γ-position of the alkyl group bonded to the free amino group. . Specific examples of the alkylation reaction include an addition reaction of an epoxy compound, an addition reaction of an aldehyde compound having a hydroxyl group or a derivative thereof at the α-position or β-position, and a subsequent reduction reaction, β-position or γ-position. Substitution reactions such as halides having 2 or more carbon atoms having a hydroxyl group or an alkoxy group, alcohols and amines are exemplified, but the invention is not limited thereto.

  In the present invention, examples of the organic compound that can be used as the alkylating reagent include aldehydes, epoxies, and phenol derivatives. Among these, a modification reaction with an epoxy compound is preferable because of its excellent reactivity and processing conditions, since it exhibits excellent characteristics. A monofunctional epoxy compound is particularly preferable.

  Specific examples of the monofunctional epoxy compound used here include, for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, octene oxide, styrene oxide, methyl styrene oxide, epichlorohydrin, epibromohydrin, glycidol and the like. Olefin oxides, glycidyl methyl ether, butyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, undecyl glycidyl ether, tridecyl glycidyl ether, pentadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether , Cresyl glycidyl ether, t-butylphenyl glycidyl ether, dibromophenyl glycidyl ether, benzyl glycidyl ether Glycidyl ethers such as polyethylene oxide glycidyl ether, glycidyl formate, glycidyl acetate, glycidyl acrylate, glycidyl methacrylate, glycidyl benzoate and the like, glycidyl amides, etc. It is not a thing.

  Among monofunctional epoxy compounds, since the water absorption rate of regenerated collagen decreases, it is preferable to treat with a monofunctional ethoxy compound represented by the following general formula (1).

但し、ＲはＲ^１−、Ｒ^２−Ｏ−ＣＨ_２−またはＲ^２−ＣＯＯ−ＣＨ_２−で表される置換基を示し、Ｒ^１は炭素数２以上の炭化水素基またはＣＨ_２Ｃｌであり、Ｒ^２は炭素数４以上の炭化水素基を示す。

R represents a substituent represented by R ¹ —, R ² —O—CH ₂ — or R ² —COO—CH ₂ —, and R ¹ represents a hydrocarbon group having 2 or more carbon atoms or CH ₂ Cl. Yes, R ² represents a hydrocarbon group having 4 or more carbon atoms.

  The regenerated collagen thus obtained is swollen with water or an aqueous solution of an inorganic salt. The swollen body preferably contains 4 to 15 times as much water or an aqueous solution of an inorganic salt as the regenerated collagen. If the content of the aqueous solution of water or inorganic salt is 4 times or more, the aluminum salt content in the regenerated collagen is large, so that the water resistance is sufficient. Moreover, if it is 15 times or less, intensity | strength does not fall and handleability is favorable.

The swollen regenerated collagen is then immersed in an aqueous solution of an aluminum salt. As an aluminum salt of this aluminum salt aqueous solution, the following formula:
Al (OH) _n Cl _3-n or Al (OH) _2n (SO ₄ ) _3-n
In the formula, n is 0.5 to 2.5.
The basic aluminum chloride or basic aluminum sulfate represented by these is preferable. Specifically, for example, aluminum sulfate, aluminum chloride, alum or the like is used. These aluminum can be used individually or in mixture of 2 or more types. The aluminum salt concentration of the aluminum salt aqueous solution is preferably 0.3 to 5% by mass in terms of aluminum oxide. When the concentration of the aluminum salt is 0.3% by mass or more, the content of the aluminum salt in the regenerated collagen fiber is high and the water resistance is sufficient. Moreover, if it is 5 mass% or less, it will not be so hard after a process, and handleability will be favorable.

  The pH of the aluminum salt aqueous solution is usually adjusted to 2.5 to 5 using, for example, hydrochloric acid, sulfuric acid, acetic acid, sodium hydroxide, sodium carbonate or the like. If this pH is 2.5 or more, the structure of collagen can be maintained well. If the pH is 5 or less, precipitation of aluminum salt does not occur, and uniform penetration is likely. This pH is first adjusted to 2.2 to 3.5, and the aluminum salt aqueous solution is sufficiently infiltrated into the regenerated collagen. Thereafter, for example, sodium hydroxide, sodium carbonate or the like is added to 3.5 to 5 It is preferable to complete the treatment by adjusting to. When a highly basic aluminum salt is used, only the first pH adjustment of 2.5 to 5 may be used. Moreover, the liquid temperature of this aluminum salt aqueous solution is although it does not specifically limit, 50 degrees C or less is preferable. If the liquid temperature is 50 ° C. or lower, the regenerated collagen is hardly denatured or altered.

  The time for immersing the regenerated collagen in this aluminum salt aqueous solution is 3 hours or more, preferably 6 to 25 hours. If this immersion time is 3 hours or more, the reaction of the aluminum salt proceeds, and the water resistance of the regenerated collagen becomes sufficient. Moreover, although there is no restriction | limiting in particular in the upper limit of immersion time, reaction of aluminum salt will fully advance within 25 hours, and water resistance will also become favorable. It should be noted that an inorganic salt such as sodium chloride, sodium sulfate, potassium chloride or the like may be appropriately added to the aqueous solution of the aluminum salt so that the aluminum salt is not rapidly absorbed into the regenerated collagen and uneven concentration occurs.

  The crosslinked regenerated collagen thus treated with the aluminum salt is then washed, oiled and dried. The regenerated collagen fiber thus obtained has almost no coloration treated with a conventional chromium salt and has excellent water resistance. In order to prevent collagen denaturation (gelatinization), attention should be paid to the temperature history during processing. In order to prevent denaturation even after cross-linking, it is necessary to keep the moisture and temperature control during production, powdering processing and product storage below the denaturation conditions of regenerated collagen. Since most of the gelatinized materials have changed characteristics, it is difficult to express the characteristics of the target collagen. It is advantageous to use the regenerated collagen in terms of degeneration.

  In the case of spinning from a collagen solution, it is easy to mix and color a pigment or dye in the solution or immediately before spinning by a known method. The pigments and dyes to be used can be selected according to the purpose, without any elution separation in the spinning process or powdering process, and according to the required quality of the product used. Moreover, a filler, an anti-aging agent, a flame retardant, an antioxidant, etc. can also be added as needed. It can replace with such a collagen fiber manufacturing process, can manufacture a film by the same method using a slit nozzle, and can also pulverize this.

  In the present invention, the regenerated collagen obtained by the above-described method can be made into a collagen powder (regenerated collagen powder) comprising regenerated collagen crosslinked by pulverization. When the regenerated collagen is a fiber or film, it is cut into a fiber length or size suitable for pulverization, further pulverized, or directly pulverized into a regenerated collagen powder. be able to. There is no particular limitation on the cutter that can be used to produce the regenerated collagen powder. For example, it is cut to about 0.1 mm to several mm with a rotary blade cutter, a belt cutter, a shearing machine, a cutter mill or the like usually used for cutting fibers. Furthermore, this cut cotton is pulverized into roller mills, rod mills, ball mills (grass wipes, wet), jet mills, pin mills, vibration mills, centrifugal (CF) mills, planetary ball mills, shearing mills such as grinder mills, etc. And finely pulverize using a medium stirring type ultrafine pulverizer. By using a hard ball such as a zirconia ball, it can be preferably used from the viewpoint of preventing the ball material from being mixed into the powder and grinding efficiency. Other material poles such as alumina balls can also be used. As another pulverization method, freeze pulverization can also be used. The regenerated collagen powder thus obtained preferably has an average particle size of 0.01 to 80 μm.

  Moreover, the content of aluminum converted as a single metal of the regenerated collagen powder is preferably in the range of 0.1 to 70% by mass. A more preferable range is 0.2 to 50% by mass, and a particularly preferable range is 1 to 40% by mass.

The regenerated collagen powder used in the present invention is obtained by finely pulverizing to an average particle size of 0.01 to 10 μm or classification after pulverization. Moreover, from a viewpoint of a touch, 0.1-10 micrometers is preferable and, as for an average particle diameter, 1-8 micrometers is more preferable. When the average particle size is larger than the above range, the surface roughness of the artificial hair is increased, resulting in a rough feel.
It is also possible to appropriately adjust the particle size of the regenerated collagen powder obtained depending on the type of pulverizer and the pulverization time. For example, when a vibration mill is used, an average particle size of about 5 to 80 μm is obtained in 1 hour to several tens of hours, but when an average particle size of 0.01 to 5 μm is obtained, crushed regeneration It is obtained by classifying collagen powder. Classification may be wind classification or classification in water.

  The average particle size of the powder after classification is preferably 10 μm or less, and 95% by mass of the particles preferably have a particle size of 50 μm or less. More preferably, the average particle size is 5 μm or less and 95% by mass of the particles have a particle size of 20 μm or less. If it is the said range, there will be no feeling of rough feeling and moisture absorption / release property is also suitable.

  The collagen powder of the present invention is excellent in whiteness. Since the collagen powder of the present invention is sufficiently refined and impurities are removed at the production stage of collagen fibers, the whiteness is high and the yellowness is low.

  The particle distribution and average particle diameter can be measured with a commercially available particle size distribution meter. For example, it can be measured using a laser diffraction / dynamic light scattering method (device name: “ELS-800” manufactured by Otsuka Electronics Co., Ltd., “MT3300” manufactured by Sakai Kisaku Co., Ltd.) etc. As a dispersion medium, for example, methanol is used. The particle refractive index is 1.44 which is the refractive index of collagen.

The regenerated collagen powder of the present invention has phosphorus adsorption ability. The phosphorus to be adsorbed is not particularly limited as long as it contains phosphorus element or a phosphorus compound. For example, a phosphate structure can be adsorbed. Here, the phosphoric acid structure means a substance having a phosphoric acid skeleton such as phosphoric acid, a phosphate, and a phosphoric ester. In general, phosphorus element is generally present in the form of a phosphoric acid structure in nature. As a preferred method for the phosphorus adsorbent of the present invention to adsorb phosphorus, an aqueous solution containing phosphorus and a regenerated collagen powder which is a phosphorus adsorbent, Alternatively, it is only necessary to mix the phosphorus adsorbent which is a mixture with the carrier. For more efficient adsorption, it is desirable to disperse the phosphorus adsorbent or adsorbent as uniformly as possible in the solution.
(2) Carpoxymethyl cellulose and polyvinyl alcohol In the present invention, carboxymethyl cellulose and polyvinyl alcohol can also be used as the organic resin powder. Carboxymethylcellulose and polyvinyl alcohol are also matrix resin gel components that are soluble in water before crosslinking, and are crosslinked by contacting an aluminum salt. The aluminum salt is chemically bonded to the gel component of the resin to form a water-insoluble resin. can do. That is, since carboxymethyl cellulose has a —COOH group and a —OH group, it can be crosslinked with an aluminum salt. Moreover, since polyvinyl alcohol has an -OH group, it can be crosslinked with an aluminum salt. Polyvinyl alcohol having a -COOH group introduced may be used. The amount of —COOH group introduced can be, for example, about 0.1 to 5 mol%.
Examples of carboxymethyl cellulose include “carboxymethyl cellulose sodium salt” manufactured by Sigma (SlGMA). An example of polyvinyl alcohol is “anion-modified PVA (A series)” grade: AF17 manufactured by Enomoto Vinegar Poval.

  The average primary particle diameter of the organic resin particles of the present invention is 0.01 μm to 10 μm, preferably 0.03 μm to 5 μm, more preferably 0.05 μm to 3 μm, and still more preferably 0.07 μm to 2 μm. is there. If the average primary particle size is in the range of 0.01 μm to 10 μm, it is preferable because the properties of the artificial hair such as the dispersibility of the root of the thermoplastic resin (A), the surface roughness of the fiber, and the touch can be balanced.

  The amount of the organic resin particles (B) used in the present invention is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, and further preferably 15 to 60 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). preferable. If the amount of the organic resin particles (B) used is in the range of 5 parts by mass or more and 80 parts by mass or less, the gloss suppression effect, moist feeling, color developability, tactile sensation, and combing are achieved, which is preferable.

  The fiber surface of the artificial hair obtained in the present invention is moderately roughened and exhibits a gloss similar to human hair. The fiber surface roughness (ten-point average roughness) Rz of the artificial hair of the present invention is preferably 0.70 to 1.50 μm, more preferably 0.75 to 1.40 μm, and further preferably 0.80 to 1.30 μm. preferable. In addition, the fiber surface roughness Rz here means the value calculated | required based on JISB0601-1994.

  Moreover, the artificial hair of this invention can provide the characteristic which is not in the past in addition to gloss suppression and a touch feeling (moist feeling) provision by including an organic resin particle. In the case of human hair, when bathing or washing (shampooing), the human hair gets wet and curls grow, and even when dried, the curl does not return to its original shape (cannot hold the curl). This phenomenon originates from the fact that the cross-linked structure inside human hair is cut (hydrolyzed) by moisture absorption and the curl shape cannot be maintained. On the other hand, synthetic fibers have low hygroscopicity and, unlike human hair, there is no change in the internal cross-linking structure due to moisture absorption and desorption, so there are some curl changes before and after shampooing, The phenomenon does not occur. On the other hand, the artificial hair of the present invention has curls stretched when moisture is absorbed and shows behavior similar to human hair, but when dried, it returns to the same curl shape as before moisture absorption and is excellent in curl retention (shampoo resistance). .

  The artificial hair of the present invention may contain various additives such as flame retardants, flame retardant aids, light stabilizers and heat stabilizers as necessary, as long as the effects of the present invention are not impaired. In particular, polyolefin fibers, polyester fibers, and polyamide fibers have lower flame retardance than acrylic fibers such as modacrylic fibers and polyvinyl chloride fibers, and therefore it is preferable to add a flame retardant and a flame retardant aid. .

  As the flame retardant, a phosphorus flame retardant and a bromine flame retardant are preferably used.

  The phosphorus-based flame retardant is not particularly limited and can be used as long as it is a commonly used brominated flame retardant. Phosphates, phosphine oxides, methanephosphonic acid esters, condensed phosphoric acid ester compounds , Phosphoric ester amide compounds, and organic cyclic phosphorus compounds. These may be used alone or in combination of two or more. Among these, condensed phosphoric ester compounds, phosphoric ester amide compounds, and organic cyclic phosphorus compounds are preferably used from the viewpoint that heat resistance and fiber physical properties are hardly lowered and sufficient flame retardancy is obtained.

  The brominated flame retardant is not particularly limited and can be used as long as it is a brominated flame retardant that is generally used. Brominated phosphoric esters, brominated polystyrenes, brominated polybenzyl acrylate , Brominated epoxy oligomers, brominated polycarbonate oligomers, tetrabromobisphenol A derivatives, bromine-containing triazine compounds, bromine-containing isocyanuric acid compounds, and the like. These may be used alone or in combination of two or more. Among these, brominated epoxy oligomers and brominated polycarbonate oligomers are preferably used from the viewpoints that the heat resistance and the physical properties of the fiber are small and sufficient flame retardancy is obtained.

  The blending ratio of the flame retardant is preferably 5 to 30 parts by mass, more preferably 6 to 25 parts by mass, and still more preferably 7 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin. When the blending ratio of the flame retardant is less than 5 parts by mass, the flame retardant effect tends to be insufficient, and when it exceeds 30 parts by mass, mechanical properties, heat resistance, and drip resistance are impaired. Tend.

  Although the flame retardancy is expressed by blending the flame retardant, the flame retardancy is remarkably improved by blending the flame retardant aid, and sufficient flame retardancy can be obtained.

  The flame retardant aid is not particularly limited, and any commonly used flame retardant aid can be used.

  Specific examples of the flame retardant aid include, for example, melamine cyanurate, antimony trioxide, antimony tetroxide, antimony pentoxide, and sodium antimonate. These may be used alone or in combination of two or more. May be.

  When the flame retardant aid is used, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and 6 parts by mass or less and 0.5 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin. Further preferred. When the usage-amount of the said flame retardant adjuvant exceeds 10 mass parts, there exists a tendency for process stability, an external appearance property, and transparency to be impaired.

  The light stabilizer is not particularly limited and can be used as long as it is generally used, but those having excellent heat resistance are particularly preferable.

  Specific examples of the light stabilizer include benzotriazole-based UV absorbers, triazine-based UV absorbers, benzophenone-based UV absorbers, benzoate-based light stabilizers, hindered amine-based light stabilizers, and the like. These compounds may be used alone or in combination of two or more. Among these, benzotriazole-based and hindered amine-based light stabilizers are more preferable from the viewpoint of heat resistance and volatile resistance.

  The blending amount of the light stabilizer is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2.5 parts by mass, and further preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the thermoplastic resin. preferable. When the blending amount of the light stabilizer is less than 0.01 parts by mass, the light resistance of the artificial hair tends to be insufficient, and when it exceeds 3 parts by mass, the spinning stability is reduced due to a decrease in melt viscosity. There is a tendency for yarn breakage to occur and mechanical properties, heat resistance, flame retardancy, and drip resistance to be impaired.

  The heat stabilizer is not particularly limited and can be used as long as it is generally used.

  Specific examples of the heat stabilizer include a hindered phenol heat stabilizer, a phosphorus heat stabilizer, a lactone heat stabilizer, an amine heat stabilizer, a vitamin E heat stabilizer, and a sulfur heat stabilizer. Can be mentioned. These compounds may be used alone or in combination of two or more. Among these, a hindered phenol heat-resistant stabilizer and a phosphorus heat-resistant stabilizer are more preferable from the viewpoint of an effect of suppressing gel generation during melt spinning.

  The blending amount of the heat stabilizer is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2.5 parts by mass, and further preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the thermoplastic resin. preferable. If the blending amount of the heat stabilizer is less than 0.01 parts by mass, a gel is generated during melt spinning, yarn breakage occurs, or a tactile sensation tends to be reduced because gel-derived protrusions remain on the fiber surface. When the amount exceeds 3 parts by mass, the spinning stability is lowered due to a decrease in melt viscosity and yarn breakage occurs, and mechanical properties, heat resistance, flame retardancy, and drip resistance tend to be impaired.

  The artificial hair in the present invention is, for example, after dry blending the thermoplastic resin (A) and the organic resin particles (B) and a flame retardant used as necessary, a flame retardant aid, a light stabilizer, a heat stabilizer, A composition obtained by melt kneading using various general kneaders can be obtained by melt spinning using a single screw extruder.

  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, as conditions for melt-kneading polytrimethylene terephthalate and regenerated collagen particles using a twin screw extruder, a twin screw extruder with a screw diameter of 45 mm is used, the barrel temperature is 200 to 240 ° C., and the discharge amount A polyester-based resin composition is obtained by melt-kneading at 50 kg / hr and a screw rotational speed of 150 rpm, taking a strand from a die, cooling with water, and pelletizing with a strand cutter. The obtained composition can be obtained by melt spinning by a usual melt spinning method. That is, for example, the temperature of an extruder, a gear pump, a die, etc. is set to 200 to 240 ° C., melt-spun, the spun yarn is passed through a heating tube, cooled to a glass transition point or less, and a speed of 100 m / min. A spun yarn can be obtained by pulling on. 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 shape is further heat-drawn, and the drawing is performed by any one of a two-step method in which an undrawn yarn is wound once and then drawn, and a direct spinning drawing method in which drawing is continuously performed without winding. 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 fiber thus obtained is colored by a dyeing method or an original deposition method.

  Further, for example, as a preferred method for fiberizing a composition comprising an acrylic resin and regenerated collagen particles, a spinning stock solution in which the copolymer is dissolved in a good solvent is prepared and coagulated with an aqueous solution containing the good solvent. The wet spinning method can be mentioned. Generally, there are a wet spinning method and a dry spinning method for fiberization of an acrylic copolymer. However, it is difficult to produce a fiber having a large fineness as in artificial hair by the dry spinning method. In the case of a wet spinning method using a good solvent, fibers with low knot strength and low elongation are easily obtained, which is preferable. This is what the present inventors have found for the first time. The good solvent is not particularly limited, but for example, at least one selected from the group consisting of dimethylformamide, dimethylsulfoxide and dimethylacetamide is used, and the acrylonitrile composition of the acrylic copolymer is soluble in a wide range. This is preferable. There are no particular restrictions on the water washing and drying conditions in the wet spinning method, but it is preferable to keep the relaxation rate after stretching and heat treatment to 3 to 15%. If the relaxation rate is in the range of 3% to 15%, the knot strength is in the range of 0.25 cN / dtex to 0.7 cN / dtex, and the knot elongation is in the range of 5% to 15%, which is preferable. The relaxation rate referred to here is the relaxation rate in the heat treatment stage of the final process for determining the fiber structure.

  The obtained fiber can be post-treated with a fiber treating agent or the like to improve touch feeling, combing property, hair unitiness, and the like. For example, surface treatment with a silicone-based fiber treatment agent for improving tactile sensation and combing, surface treatment with a non-silicone fiber treatment agent, and the like can be mentioned.

  The fineness of the artificial hair of the present invention thus obtained is preferably 10 to 100 dtex, more preferably 20 to 90 dtex, from the viewpoint of suitability for artificial hair.

  The headdress product of the present invention refers to hair wigs, two-pees, weaving, hair extensions, blades, hair accessories, doll hairs, etc., produced using the artificial hair of the present invention.

  The artificial hair of the present invention is formed using fibers containing the thermoplastic resin (A), and the gloss is moderately suppressed by the unevenness of the fiber surface formed by the organic resin particles (B) in the present invention. It is a thing. Artificial hair made of polyester resin or polyamide resin is excellent in curl setting using a beauty heat instrument, excellent in curl retention, and is formed by the cellulose compound in the present invention. Gloss is moderately suppressed by the unevenness of the fiber surface.

  Specifically, the artificial hair of the present invention is suitable for processing into hair ornament products such as hair wigs, two-pieces, weaving, hair extensions, blades, hair accessories, doll hair, and the like (gloss, hue) ) And a soft tactile sensation, and also has excellent curling characteristics.

  Hair wigs are ornaments that are attached to the head, regardless of whether they are for women or gentlemen, and are mainly for enjoying fashion. Depending on the mounting surface, partial wigs, half wigs, seven-minute wigs, Divided into full wigs.

  On the other hand, “Tupe” is a generic term for wigs that are used mainly for gentlemen or on the entire head, and is a headdress product produced by implanting artificial hair into a pseudo scalp.

  A method for processing these head ornament products using the artificial hair of the present invention can be performed by a known production method. For example, when making a hair wig, sew it with the fiber bundle wig sewing machine to make eyelashes, wind this around a pipe, add curl with a steam set, and sew the curled eyelashes to the hair cap. Can be made by arranging the style.

  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 and evaluation are as follows.
(Fiber surface roughness)
In this invention, the magnitude | size of the processus | protrusion which exists in the fiber surface calculates | requires ten-point average roughness (Rz) with the laser microscope (Keyence VK-9500). The fiber side is measured at a magnification of 3000 times (objective lens 150 times x built-in lens 20 times) and 10 parallel to the fiber axis, and the obtained image is calculated according to the surface roughness definition of JIS B0601-1994. Calculated based on
(Average primary particle size)
The average primary particle diameter of the present invention refers to the average primary particle diameter of organic resin particles obtained by a dynamic light scattering method, and is a value measured by a light scattering photometer (device name: Otsuka Electronics Co., Ltd. ELS-800). Is adopted. The average primary particle diameter of the regenerated collagen particles obtained by this method is as follows. The regenerated collagen particles are dispersed at 0.5 wt% in dimethylformamide in a constant temperature and humidity chamber adjusted to 25 ° C. and 55% RH, and placed in a sonicator for 10 minutes. It is obtained by measuring what is multiplied.
(Antibacterial)
As a test sample, a tow filament was thinly spread to a width of 5 cm, cut to a length of 5 cm, and used for an antibacterial test. In the test, Escherichia coli F03972 was cultured in 5 ml of normal bouillon medium (Eiken Chemical Co., Ltd.) at 27 ° C. with shaking overnight, and then sterilized physiological saline (0. Diluted with 85 wt% NaCl). 0.4 ml of this bacterial suspension was placed in a resin petri dish (manufactured by Seibu Co., Ltd.), a sample was placed on this bacterial solution with the test surface down, covered, and allowed to stand at 30 ° C. At the time of inoculation and 24 hours later, this bacterial suspension was recovered in 4.5 ml of sterile physiological saline, diluted 10 times by 5 steps, and the number of viable bacteria in 0.5 ml of these bacterial suspensions was measured. For the control, a polyethylene sheet was used instead of the sample, and the same operation was performed. The number of viable bacteria was measured according to the hygiene test method, comment (2005) 1.2.1.1.1.1 general bacteria test method 3) fungus measurement (1) pour plate culture method (p. 59). However, SCDLP agar medium “DAIGO” (manufactured by Nippon Pharmaceutical Co., Ltd.) was used for culturing the microorganisms and cultured for 24 hours at 37 ° C. The viable cell count was the viable cell count concentration in the cell suspension inoculated into the sample. The evaluation criteria for the detection limit of viable cell count converted to ≦ 10 ² / m1 are as follows.
A: Not detected B: Viable count 1 × 10 ² cells / ml or more and less than 4 × 10 ⁶ cells / ml C: Viable cell count 4 × 10 ⁶ cells / ml or more (fiber gloss)
A tow filament having a length of 30 cm and a total fineness of 100,000 dtex was visually evaluated according to the following criteria under sunlight.
A: Gloss that cannot be recognized as a difference from human hair even if carefully compared. B: Gloss that can be judged to be more or less glossy than human hair when carefully compared. C: Gloss that can be judged to be more or less glossy than human hair when compared with normal attention, in contrast D: Clearly too glossy than human hair without requiring comparison, or , Gloss that can be judged to be too little (feel)
A tow filament having a length of 30 cm and a total fineness of 100,000 dtex was touched by hand to evaluate the feel of the filament surface.
A: There is a moist feeling and is a touch feeling very close to human hair B: There is a slightly moist feeling and a touch feel close to human hair C: There is a dry feeling D: There is a dry feeling, a squeaky feeling (waxy feeling) ( Extensibility when wet)
The filaments (30 cm) made into eyelashes are placed on a 32 mmφ pipe, curled for 60 minutes at each temperature of 70 to 140 ° C., aged at room temperature for 60 minutes, then the pipe is removed and the curled eyelashes (12 cm ) Next, the filament was immersed in hot water at 40 ° C. for 10 minutes, then taken out, drained, the filament length was measured, and compared with the eyelash length before curling, the extensibility when wet was evaluated.
[Extension] = (Filament length when wet) / [Filament length before curl setting (30 cm)]
A: Extensibility exceeds 0.75 B: Extensibility is 0.75 to 0.60
C: Extensibility is 0.60 to 0.50
D: Extensibility is less than 0.50 (curl retention)
Using the eyelashes obtained in the same manner as described above, the eyelashes were immersed in hot water at 40 ° C. for 5 minutes and then taken out and then air-dried. The change in filament length after repeating this operation 5 times was examined, and the curl retention (elongation rate) was evaluated.
[Elongation rate (%)] = [(Filament length after 5 times wet / dry) − (Initial filament length)] / (Initial filament length) × 100
A: Elongation rate is less than 15% B: Elongation rate is 15-30%
C: Elongation rate is 30-50%
D: Elongation rate exceeds 50% The raw materials used in the examples and comparative examples are as follows (excluding those exemplified in the examples and comparative examples).
Polyester A: Polytrimethylene terephthalate, manufactured by Shell Chemicals, Cortera CP509201
Polyester B: Polyethylene terephthalate, manufactured by Mitsubishi Chemical Corporation, BK-2180
Flame retardant: Brominated epoxy flame retardant, Sakamoto Pharmaceutical Co., Ltd., SR-T20000
Silica: manufactured by UNIMIN, Imsil A-8 (average particle size of 2 to 3 μm)
Cross-linked acrylic resin particles: MR-2HG (average particle size 2 μm), manufactured by Soken Chemical Co., Ltd.
Colorant: Pigment master batch, containing 20 wt% carbon black, manufactured by Dainichi Seika Kogyo Co., Ltd., PESM6100BLACK
(Production Examples 1 to 5) Production of regenerated collagen powder After using 30 g of hydrogen peroxide aqueous solution diluted to 30% by mass to 1200 kg (collagen content: 180 kg) of cow's floor skin as raw material, A stock solution was prepared by dissolving in an aqueous lactic acid solution and adjusting the pH to 3.5 and the solid content to 7.5% by mass. The stock solution was subjected to a stirring frame defoaming treatment with a stirring defoamer (8DMV type manufactured by Dalton Co., Ltd.) under reduced pressure, transferred to a piston-type spinning stock solution tank, and further allowed to stand under reduced pressure for defoaming. The stock solution is extruded with a piston, and then is fed in a fixed amount by a gear pump, filtered through a sintered filter having a pore diameter of 10 μm, passed through a spinning nozzle having a pore diameter of 0.275 mm, a pore diameter of 0.5 mm, and a pore number of 300, and 20 mass of sodium sulfate. % Was discharged at a spinning speed of 5 m / min into a 25 ° C. coagulation bath (adjusted to pH 11 with boric acid and sodium hydroxide).

  Next, 1.32 kg of an aqueous solution containing 1.7% by mass of epichlorohydrin, 0.0246% by mass of sodium hydroxide, and 17% by mass of sodium sulfate was obtained from the obtained regenerated collagen woven spine (300, 20 m). After being immersed in the solution at 25 ° C. for 4 hours, the temperature of the reaction solution was further increased to 43 ° C. and impregnated for 2 hours.

  After completion of the reaction, the reaction solution was removed, and then washed with batch water three times using 1.32 kg of 25 ° C. water in a fluid type apparatus. Thereafter, it was impregnated at 30 ° C. with 1.32 kg of an aqueous solution containing 5% by weight of aluminum sulfate, 0.9% by weight of trisodium citrate, and 1.2% by weight of sodium hydroxide. After 5 hours and 4 hours, 13.2 g of a 5 mass% sodium hydroxide aqueous solution was added to the reaction solution, and the reaction was performed for a total of 6 hours. After completion of the reaction, the reaction solution was removed, and then washed with batch water three times using 1.32 kg of 25 ° C. water in a fluid type apparatus.

  Next, a part of the prepared fiber was immersed in a bath filled with an oil agent comprising an amino-modified silicone emulsion and a pluronic polyether-based antistatic agent to adhere the oil agent. One end of the fiber bundle was fixed inside a hot air convection dryer set at 50 ° C., and a weight of 2.8 g was suspended from one fiber on the other end and dried under tension for 2 hours. Regenerated collagen fibers were obtained.

The obtained regenerated collagen fiber was physically pulverized. That is, first, 2 kg of regenerated collagen fibers were shredded to a length of about 1 mm with a cutter mill SF-8 (manufactured by Sanriki Seisakusho) and recovered with a Cyclone CYC-600 model manufactured by the same company. Next, it grind | pulverized using the vibration mill (made by Token Co., Ltd.). As the grinding conditions, the same alumina balls (diameter 19 mm) are filled in an alumina container having a capacity of 4 L at a filling capacity of 80%, and the chopped collagen fibers are filled in a filling capacity of 40% (500 g) for 4 to 12 hours. Carried out. As a result, it was possible to obtain a powder having an average particle size of 33 μm by pulverization for 4 hours and an average particle size of 10 μm by pulverization for 15 hours. This powder having an average particle diameter of 10 μm was classified by wind to obtain powders having the following average particle diameters A to E.
Organic resin particles A: regenerated collagen particles, particle size 1.0 μm
Organic resin particles B: regenerated collagen particles, particle size 0.05 μm
Organic resin particles C: regenerated collagen particles, particle size 3.0 μm
Organic resin particles D: regenerated collagen particles, particle size 0.005 μm
Organic resin particles E: regenerated collagen particles, particle size 11 μm
(Production Example 6) Production of polyvinyl alcohol (PVA) powder An insolubilized PVA powder was produced as follows. A 10% (W / V) aqueous solution of anion-modified polyvinyl alcohol (trade name “AF-17” manufactured by Nihon Ventures and Poval Co., Ltd.) was prepared, and the solution was added dropwise to an aluminum sulfate solution for cross-linking aluminum to remove insoluble matter. Formed. The insoluble material was collected, dried, and pulverized in a mortar to obtain fine particles. The fine particles were classified to cut particles having a size of 20 μm or more, and a fine powder having an average particle size of 11 μm was obtained. The fine powder was classified by wind to obtain a powder having the following F average particle diameter.
Organic resin particles F: polyvinyl alcohol particles, particle size 1.0 μm
(Production Example 7) Production of insolubilized carboxymethylcellulose (CMC) powder A 1% by mass aqueous solution of carboxymethylcellulose sodium salt (CMC; manufactured by Sigma) was produced, and the solution was added dropwise to an aluminum sulfate solution for aluminum cross-linking so as to be insoluble. Formed. The insoluble material was collected, dried, and pulverized in a mortar to obtain fine particles. This fine powder was classified by wind to obtain a powder having the following G average particle diameter.
Organic resin particles G: carboxymethylcellulose particles, particle size 1.0 μm
(Examples 1-9)
A composition having a blending ratio shown in Table 1 was dried to a water content of 100 ppm or less, dry-blended, and then supplied to a twin-screw extruder (manufactured by Nippon Steel Works, Ltd., TEX44) at a barrel set temperature of 280 ° C. After melt-kneading and pelletizing, it was dried to a water content of 100 ppm or less. Next, using a melt spinning machine (SV30, manufactured by Shinko Machinery Co., Ltd.), a spinneret (set temperature: 280 ° C.) having a vertical cross-section nozzle hole with a flat ratio of 1.4: 1 at a barrel set temperature of 280 ° C. More molten polymer was discharged, air-cooled with 20 ° C. cooling air, and wound 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 Polyester artificial hair having a fineness of about 50 dtex was obtained.

  KWC-Q (Random copolymer polyether of ethylene oxide-propylene oxide; manufactured by Maruhishi Yuka Co., Ltd.) / Processing agent 29 (cationic surfactant) Manufactured by Maruhishi Oil Chemical Co., Ltd.) = 0.10 / 0.05% omf, an aqueous solution was prepared, and a tow filament having a total fineness of 100,000 dtex was mixed with a liquid content of 25% based on the weight of the tow. Then, the solution was adhered so that it was dried at 120 ° C. for 10 minutes using a hot air dryer.

得られた人工毛髪を用いて、表面粗さ、抗菌性、光沢、触感、湿潤時の伸長性、カール保持性を評価した結果を、表２に示す。

Table 2 shows the results of evaluating the surface roughness, antibacterial properties, gloss, touch, extensibility when wet, and curl retention using the obtained artificial hair.

（実施例１０〜１９）
塩化ビニル系樹脂、塩素化塩化ビニル系樹脂、安定剤、滑剤、添加剤を所定の割合で、
ヘンシェルミキサーで攪拌混合し、コンパウンドを製造した（表３）。塩化ビニル系樹脂は、（株）カネカ製のＳ１００１を、塩素化塩化ビニル系樹脂は、（株）カネカ製のＨ４３８を使用した。安定剤は、協和化学株式会社製のハイドロタルサイト熱安定剤であるアルカマイザー１を１重量部、糸の触感を向上させるＥＶＡ系樹脂については、日本ユニカー（株）製のＰＥＳ−２５０を１０部、アクリル系加工助剤として（株）カネカ製のＰＡ−２０を０．３部、エステル系滑剤として、理研ビタミン（株）社製ＥＷ−１００を０．５重量部、ポリエチレンワックス系滑剤として三井化学（株）社製ＨＷ４００Ｐを０．５重量部添加した。４０ｍｍφ押し出し機に、孔断面積０．１ｍｍ²、孔数１２０個のノズルを取り付けた。孔形状は６基線形状と瓢箪形状の２種類とし、孔数９０個については６基線形状孔数３０個については、瓢箪形状とした。シリンダー温度１４０〜１９０℃、ノズル温度１８０±１５℃の範囲で、紡糸性の良い条件で上記コンパウンドを押し出し溶融紡糸した。押し出されたフィラメントをノズル直下に設けた加熱紡糸筒内（２００〜４００℃雰囲気で紡糸性の良い条件）で約０．５〜１．５秒熱処理し、第一の引き取りロールによって紡糸した。この第一引き取りロールの直前で油剤を、最終製品重量に対して油剤純分の重量分率が０．２重量％になるように添付した。次に、第二の延伸ロールとの間で１１０℃の熱風循環箱を通して３倍程度に延伸した。さらに１１０℃に温度調整した箱の中に設置した２対の円錐形ロール間を引き回し、連続的に約３０％緩和処理を実施し、単繊維繊度７５ｄｔｅｘの塩化ビニル系人工毛髪を得た。

(Examples 10 to 19)
Vinyl chloride-based resin, chlorinated vinyl chloride-based resin, stabilizer, lubricant, additive at a predetermined ratio,
The mixture was stirred and mixed with a Henschel mixer to produce a compound (Table 3). S1001 manufactured by Kaneka Corporation was used as the vinyl chloride resin, and H438 manufactured by Kaneka Corporation was used as the chlorinated vinyl chloride resin. The stabilizer is 1 part by weight of Alkamizer 1 which is hydrotalcite heat stabilizer manufactured by Kyowa Chemical Co., Ltd., and 10% of PES-250 manufactured by Nihon Unicar Co., Ltd. is used for EVA resin which improves the feel of yarn. Part, PA-20 manufactured by Kaneka Co., Ltd. as an acrylic processing aid, 0.3 parts ester lubricant, 0.5 parts by weight EW-100 manufactured by Riken Vitamin Co., Ltd. as polyethylene wax lubricant 0.5 part by weight of HW400P manufactured by Mitsui Chemicals, Inc. was added. A nozzle having a hole cross-sectional area of 0.1 mm ² and a hole number of 120 was attached to a 40 mmφ extruder. There are two types of hole shapes, a 6-baseline shape and a bowl shape, with a 90-hole shape and a 30-hole 6-baseline hole shape. The compound was extruded and melt-spun in a range of a cylinder temperature of 140 to 190 ° C. and a nozzle temperature of 180 ± 15 ° C. under good spinning properties. The extruded filament was heat treated for about 0.5 to 1.5 seconds in a heated spinning cylinder (under 200 to 400 ° C. atmosphere and good spinnability) provided immediately below the nozzle, and spun by a first take-up roll. Immediately before this first take-up roll, the oil was attached so that the weight fraction of the pure oil was 0.2% by weight with respect to the final product weight. Next, it extended | stretched about 3 times through the 110 degreeC hot-air circulation box between the 2nd extending | stretching rolls. Furthermore, it was drawn between two pairs of conical rolls installed in a box whose temperature was adjusted to 110 ° C., and subjected to a relaxation treatment of about 30% continuously to obtain a vinyl chloride artificial hair having a single fiber fineness of 75 dtex.

  To the obtained artificial hair, an aqueous solution was prepared so that the hydrophilic fiber treatment agent KWC-Q / processing agent 29 = 0.10 / 0.05% omf, and the tow filament having a total fineness of 100,000 dtex was prepared. The solution was adhered so that the liquid content was 25% with respect to the tow weight, and dried at 120 ° C. for 10 minutes using a hot air dryer.

得られた人工毛髪を用いて、表面粗さ、抗菌性、光沢、触感、湿潤時の伸長性、カール保持性を評価した結果を、表４に示す。

Table 4 shows the results of evaluating the surface roughness, antibacterial properties, gloss, touch, stretchability when wet, and curl retention using the obtained artificial hair.

（実施例２０、２１）
相対粘度が２．５０のナイロン６と有機樹脂粒子Ａをナイロン６／有機樹脂粒子Ａ／着色剤（ＰＡＭ６１００ＢＬＡＣＫ、大日精化工業（株）製、顔料マスタバッチ、カーボンブラック２０ｗｔ％含有）＝１００／３０／２の混合比でドライブレンドし、２軸押出機に投入し、２６０℃の条件で均一に混練し、ペレット状に溶融混練した。このペレットを、溶融温度２６０℃で溶融し、紡糸口金（６８孔）より紡糸を行い、２１０℃の雰囲気温度の加熱フード（長さ１８０ｍｍ）中に糸条を紡出した。その後、この糸条に温風吹き付け装置（吹き付け部の長さ１５０ｍｍ）より９０℃の温風を吹き付け、次に２０℃の冷却風を吹き付け、冷却固化させた。その後、油剤を付与し、３０００ｍ／分の引取ローラで引き取り、ローラ間で０．５％伸長した後捲き取り、単繊維繊度５０ｄｔｅｘのポリアミド系人工毛髪を得た。

(Examples 20 and 21)
Nylon 6 and organic resin particle A having a relative viscosity of 2.50 are nylon 6 / organic resin particle A / colorant (PAM6100BLACK, manufactured by Dainichi Seikagaku Co., Ltd., pigment master batch, containing 20 wt% carbon black) = 100 / Dry blending was performed at a mixing ratio of 30/2, charged into a twin screw extruder, uniformly kneaded at 260 ° C., and melt-kneaded into pellets. The pellets were melted at a melting temperature of 260 ° C., spun from a spinneret (68 holes), and the yarn was spun into a heating hood (length: 180 mm) at an ambient temperature of 210 ° C. Then, 90 degreeC warm air was sprayed on this yarn from the warm air spraying apparatus (the length of the spraying part 150 mm), and then 20 degreeC cooling air was sprayed and solidified by cooling. Thereafter, an oil agent was applied, taken up with a take-up roller of 3000 m / min, and stretched by 0.5% between the rollers, and then scraped off to obtain a polyamide artificial hair having a single fiber fineness of 50 dtex.

  To the obtained artificial hair, an aqueous solution was prepared so that the hydrophilic fiber treatment agent KWC-Q / processing agent 29 = 0.10 / 0.05% omf, and the tow filament having a total fineness of 100,000 dtex was prepared. The solution was adhered so that the liquid content was 25% based on the tow weight, and dried at 120 ° C. for 10 minutes using a hot air dryer (Example 20).

  Similarly, polyamide-based artificial hair having a single fiber fineness of 52 dtex was obtained using the organic resin particles C (Example 21).

  Table 5 shows the results of evaluating the surface roughness, antibacterial properties, gloss, touch, stretchability when wet, and curl retention using the obtained artificial hair.

（実施例２２、２３）
ポリプロピレンホモポリマー（日本ポリプロ社製ＳＡ０３、融点１６５℃）と有機樹脂粒子Ａをポリプロピレンホモポリマー／有機樹脂粒子Ｃ／着色剤（ＰＡＭ６１００ＢＬＡＣＫ、大日精化工業（株）製、顔料マスタバッチ、カーボンブラック２０ｗｔ％含有）＝１００／５０／２の混合比でドライブレンドし、２軸押出機に投入し、２２０℃の条件で均一に混練し、ペレット状に溶融混練した。このペレットを、押出機温度２２５℃、紡糸ノズル温度２２５℃とし、溶融押出機の１軸押出機に投入し、ホール径０．６ｍｍ、ホール数４８の紡糸ノズルよりポリマーを吐出し、巻取速度４００ｍ／分で巻き取り未延伸糸を得た。この未延伸糸を温度８０℃のローラーにて最終延伸速度４００ｍ／分で３．２４倍に延伸し、単繊維繊度６５ｄｔｅｘのポリプロピレン系人工毛髪を得た。

(Examples 22 and 23)
Polypropylene homopolymer (SA03 manufactured by Nippon Polypro Co., Ltd., melting point 165 ° C.) and organic resin particles A were combined with polypropylene homopolymer / organic resin particles C / colorant (PAM6100BLACK, manufactured by Dainichi Seikagaku Co., Ltd., pigment master batch, carbon black 20 wt. % Contained) = 100/50/2, and dry blended, put into a twin screw extruder, uniformly kneaded at 220 ° C., and melt-kneaded into pellets. The pellets were set to an extruder temperature of 225 ° C. and a spinning nozzle temperature of 225 ° C., and were put into a single screw extruder of a melt extruder, and a polymer was discharged from a spinning nozzle having a hole diameter of 0.6 mm and a hole number of 48, and the winding speed was A wound undrawn yarn was obtained at 400 m / min. This undrawn yarn was drawn 3.24 times with a roller at a temperature of 80 ° C. at a final drawing speed of 400 m / min to obtain a polypropylene-based artificial hair having a single fiber fineness of 65 dtex.

  To the obtained artificial hair, an aqueous solution was prepared so that the hydrophilic fiber treatment agent KWC-Q / processing agent 29 = 0.10 / 0.05% omf, and the tow filament having a total fineness of 100,000 dtex was prepared. The solution was adhered so that the liquid content was 25% based on the weight of the tow, and dried at 120 ° C. for 10 minutes using a hot air dryer (Example 22).

  Similarly, using the organic resin particles C, a polyamide-based artificial hair having a single fiber fineness of 52 dtex was obtained (Example 23).

Table 5 shows the results of evaluating the surface roughness, antibacterial properties, gloss, touch, stretchability when wet, and curl retention using the obtained artificial hair.
(Examples 24 to 30)
Acrylic copolymer produced by emulsion polymerization, 54% by mass, 44% by mass of vinylidene chloride, and 2% by mass of 2-acrylamido-2-methylpropane sulfonic acid sodium and organic resin particles are mixed with dimethyl at a predetermined mixing ratio. It was dissolved in formamide (hereinafter referred to as DMF) to produce a 28% by mass spinning dope (Table 6). This spinning dope was spun into a 60 wt% DMF aqueous solution (temperature 20 ° C.) with a nozzle draft coefficient of 0.9 through a spinning nozzle having a hole diameter of 0.3 mmφ and a hole number of 50 holes, and then 45 ° C. and 30 wt%. It led to the bath which consists of DMF aqueous solution, and extended | stretched 2.7 times, and also extended | stretched 1.5 times in the bath which consists of 70 degreeC and 15 weight% DMF aqueous solution. Subsequently, it was washed with water at 90 ° C., dried at 145 ° C., then stretched 1.5 times, and subjected to 10% relaxation treatment at 120 ° C. in a steam atmosphere to obtain acrylic artificial hair having a fineness of 58 dtex.
To the obtained artificial hair, an aqueous solution was prepared so that the hydrophilic fiber treatment agent KWC-Q / processing agent 29 = 0.10 / 0.05% omf, and the tow filament having a total fineness of 100,000 dtex was prepared. The solution was adhered so that the liquid content was 25% with respect to the tow weight, and dried at 120 ° C. for 10 minutes using a hot air dryer.

得られた人工毛髪を用いて、表面粗さ、抗菌性、光沢、触感、湿潤時の伸長性、カール保持性を評価した結果を、表７に示す。

Table 7 shows the results of evaluating the surface roughness, antibacterial properties, gloss, touch, stretchability when wet, and curl retention using the obtained artificial hair.

（比較例１〜６）
表８に示す配合比率の組成物を、実施例と同様にして、各種人工毛髪を得た。

(Comparative Examples 1-6)
Various artificial hairs were obtained in the same manner as in Examples with compositions having the blending ratios shown in Table 8.

得られた人工毛髪を用いて、表面粗さ、抗菌性、光沢、触感、湿潤時の伸長性、カール保持性を評価した結果を、表９に示す。

Table 9 shows the results of evaluating the surface roughness, antibacterial properties, gloss, touch, stretchability when wet, and curl retention using the obtained artificial hair.

表２、表４、表５、表７および表９に示したように、比較例に対し、実施例では、有機樹脂粒子を使用することにより、人毛に近い光沢感、自然な人毛に似た毛質感（しっとり感）、抗菌性を有し、カール保持性に優れた人工毛髪が得られることが確認された。従って、今回の組成物を使用した人工毛髪は、従来の人工毛髪に比べ、光沢、毛質感がより人毛に近づいており、ヘアーウィッグやツーペ等頭飾製品として使用した場合に、人毛と一緒に用いても違和感がないものであり、人工毛髪、頭飾製品として有用なものであることが証明された。

As shown in Table 2, Table 4, Table 5, Table 7 and Table 9, in comparison with the comparative examples, in the examples, by using organic resin particles, glossiness close to human hair, natural human hair It was confirmed that artificial hair having a similar hair texture (moist feeling), antibacterial properties and excellent curl retention was obtained. Therefore, the artificial hair using the composition of this time is closer to human hair in terms of luster and hair texture than conventional artificial hair, and together with human hair when used as hair ornaments such as hair wigs and two-pews. It was proved to be useful as artificial hair and hair ornament products.

Claims (10)

  For artificial hair, characterized in that it is formed from a composition containing 100 parts by mass of thermoplastic resin (A) and 5-80 parts by mass of organic resin particles (B) having an average primary particle size of 0.01 μm to 10 μm. fiber.   The thermoplastic resin (A) is one or more polymers selected from the group consisting of polyolefin resins, polyvinyl chloride resins, acrylic resins, polyester resins and polyamide resins. The fiber for artificial hair as described.   The fiber for artificial hair according to claim 1 or 2, wherein the organic resin particles (B) are at least one organic resin selected from regenerated collagen, polyvinyl alcohol, and carboxymethylcellulose.   The fiber for artificial hair according to claim 3, wherein the organic resin particles (B) are crosslinked with an aluminum salt. The fiber for artificial hair according to claim 4, wherein the organic resin particles (B) contain a crosslinking component, and the crosslinking component is a monofunctional epoxy compound represented by the general formula (1).

(However, R represents a substituent represented by R ¹ —, R ² —O—CH ₂ —, or R ² —COO—CH ₂ —, and R ¹ represents a hydrocarbon group having 2 or more carbon atoms or CH _2. Cl and R ² is a hydrocarbon group having 4 or more carbon atoms.) The fiber for artificial hair according to claim 5, wherein the aluminum salt is represented by the following formula.
Al (OH) _n Cl _3-n or Al ₂ (OH) _2n (SO ₄ ) _3-n
(However, n = 0.5 to 2.5)   The fiber surface roughness (ten-point average roughness) Rz is 0.70 to 1.50 µm, The artificial hair fiber according to any one of claims 1 to 6.   Artificial hair obtained using the fiber for artificial hair according to any one of claims 1 to 7.   A headdress product obtained by processing the artificial hair according to claim 8.   The headdress product according to claim 9, wherein the headdress product is a weaving, a wig, a two-piece, a hair extension, or a hair accessory.