WO2012157561A1 - Fiber for artificial hair, and hairpiece product - Google Patents
Fiber for artificial hair, and hairpiece product Download PDFInfo
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- WO2012157561A1 WO2012157561A1 PCT/JP2012/062133 JP2012062133W WO2012157561A1 WO 2012157561 A1 WO2012157561 A1 WO 2012157561A1 JP 2012062133 W JP2012062133 W JP 2012062133W WO 2012157561 A1 WO2012157561 A1 WO 2012157561A1
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- fiber
- artificial hair
- ratio
- temperature
- elastic modulus
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41G—ARTIFICIAL FLOWERS; WIGS; MASKS; FEATHERS
- A41G3/00—Wigs
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41G—ARTIFICIAL FLOWERS; WIGS; MASKS; FEATHERS
- A41G3/00—Wigs
- A41G3/0083—Filaments for making wigs
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
Definitions
- the present invention relates to a fiber for artificial hair and a hair product using the same.
- artificial hair made of synthetic fibers has been used for hair products such as wigs and hair wigs.
- artificial hair is often straight hair as it is, in recent years, fibers for artificial hair that can be processed, such as curling, have been demanded from the expansion of fashion usage of artificial hair.
- Examples of the artificial hair fibers excellent in curl setting include flame retardant polyester artificial hair (see Patent Document 1). Since this artificial hair fiber has high heat resistance, it can be heated at high temperature with a hair iron or the like and has excellent curling properties.
- the main object of the present invention is to provide a fiber for artificial hair having high processability such as curling.
- the present invention is to provide a product using the fiber for artificial hair and the artificial hair fibers, storage modulus at 90 and 0.99 ° C. 'storage modulus E at 90 ° C. in a' storage modulus E with respect to temperature 90 / E '0.99' ratio E of 0.99 'E is 3 to 20 fiber for artificial hair.
- the curve of the storage elastic modulus E ′ with respect to the temperature has a glass state region where the storage elastic modulus E ′ is constant and a transition region where the rate of change is maximum at a higher temperature than the glass state region.
- the artificial hair fiber is more preferably produced from a resin composition containing as a main component either one or both of a polyester resin and a polyamide resin.
- the resin composition is a fiber for artificial hair produced by melt-discharging the resin composition from a nozzle hole to produce an unstretched yarn, and then stretching the unstretched yarn. It is more preferable that the ratio D 1 / D 2 between the magnification D 1 stretched during the production and the magnification D 2 stretched during the stretching process is 1.5 to 14.0.
- a hair product can also be produced using the artificial hair fibers.
- the present invention provides a fiber for artificial hair that is excellent in curling properties (styling properties, setting properties).
- Artificial hair fibers are not particularly limited, and are, for example, synthetic fibers obtained by spinning a resin composition, or synthetic fibers obtained by attaching a treatment agent or the like.
- the forming process may be performed by either the artificial hair fiber manufacturer, the hair product processor, or the end consumer who purchased the hair product.
- a manufacturer of artificial hair fibers or hair products performs a molding process such as curling on the artificial hair fibers before market.
- the forming process may be performed at any stage before the artificial hair fiber is processed into a hair product, during the processing of the hair product, or after the processing into the hair product.
- the forming process is not limited to curling (wave), and includes cases where the wave is straight (straight hair).
- the forming method is not particularly limited, and a method of bringing a heating device such as a hair iron into contact (pressing) with the artificial hair fiber, or exposing the artificial hair fiber to hot air in a state of being wound around a core (such as a metal tube).
- a heating device such as a hair iron into contact (pressing) with the artificial hair fiber
- exposing the artificial hair fiber to hot air in a state of being wound around a core such as a metal tube.
- a method a method of heating the winding core itself, and the like.
- a method in which a winding core wound with artificial hair fibers is placed in a heating furnace (oven) and heated is used.
- the heating temperature for molding is not particularly limited, and can be appropriately changed depending on the raw material of the fiber for artificial hair, but is generally in the range of 90 to 150 ° C. (molding temperature region).
- FIG. 1 is a schematic diagram for explaining viscoelastic properties of artificial hair fibers. Synthetic fibers are reduced in both storage elastic modulus E ′ and loss elastic modulus E ′′ by heating, and the larger the change rate, the easier the deformation of curls and the like. In the oven curl temperature region of FIG. 1, those having a large change rate are suitable for artificial hair fibers.
- E 1 is a change curve of the elastic modulus (E ′, E ′′) of a commercially available heat-resistant artificial hair. Since the heat-resistant artificial hair has heat resistance, the elastic modulus at the molding temperature (E ′, E ′′). ) Is small, and curl and other moldability are poor. If the elastic modulus (E ′, E ′′) changes greatly at the molding temperature as indicated by reference symbols a and b in FIG. 1, it easily deforms at the molding temperature and the moldability is good.
- Changes in the elastic modulus (E ′, E ′′) at the molding temperature can be adjusted by changing the composition of the resin composition used as the raw material for artificial hair fibers.
- a thermoplastic resin having a low glass transition temperature can be used. If the main raw material is used, the elastic modulus (E ′, E ′′) can be greatly changed at the molding temperature, but the heat resistance is poor.
- the end consumer may process the hair product according to personal preference (post-molding).
- post-molding commercially available heating appliances (hair irons, etc.) are often used, and the heating temperature varies from 60 to 240 ° C. There is a tendency of higher temperature (180 to 240 ° C., post-molding temperature region) than the molding process of No. 1.
- the material does not melt before reaching the post-molding temperature region and has a large change rate in the molding temperature region and the post-molding temperature region.
- the change in the elastic modulus (E ′, E ′′) is large even when melted, a and c in FIG. 1 are melted in the post-molding temperature region, and b is melted before reaching the post-molding temperature region. Since the artificial hair fibers are not heated at a high temperature exceeding the post-heating temperature region, if the rate of change is large in the post-molding temperature region, melting occurs in that region as in a and c. It doesn't matter.
- the molding temperature often used in the field of artificial hair is in the range of 90 to 150 ° C.
- the post molding temperature preferred by consumers is in the range of 180 to 240 ° C., that is, the elastic modulus changes greatly in these regions. .
- temperature (° C.) 90 / E '150' ratio E of 150 '90 and 150 ° C. storage modulus E at' the storage modulus E at 90 ° C. in 'the storage modulus E with respect is 3-20 More preferably, it is 4 to 10.
- E ′ 90 / E ′ 150 is less than 3, the change in elastic modulus in the molding temperature region (90 to 150 ° C.) is small, so that curling is difficult and curling properties are poor.
- E ′ 90 / E ′ 150 exceeds 20, the fiber contracts, resulting in poor curling properties.
- E ′ 90 / E ′ 150 is 4 to 10, it is particularly preferable because excellent curling properties can be realized without shrinking the fibers.
- the deformation temperature at which the glass state of the crystal collapses is in the range of 180 to 240 ° C. It is desirable to be.
- the deformation temperature is, for example, a tangent line passing through a region (glass state region) where the storage elastic modulus is constant in the storage elastic modulus curve, and a transition region where the change rate of the storage elastic modulus is the highest on the higher temperature side. It is the temperature at which the intersection with the tangent line passing through (or the transition point where the rate of change of the storage elastic modulus is the largest) is located.
- the artificial hair fiber satisfying the temperature and viscoelasticity as described above can be produced, for example, by appropriately adjusting the fiber production conditions and the blending of the raw materials.
- the resin composition contains a thermoplastic resin as a main component (content of 50% by mass or more) and contains additives such as a flame retardant, a filler, a colorant, and an anti-aging agent as necessary.
- Viscoelasticity (E ′, E ′′, etc.) can be adjusted by, for example, the blending ratio of two or more thermoplastic resins or the blending ratio of the thermoplastic resin and additives (flame retardant, filler, etc.).
- By blending two or more thermoplastic resins having different glass transition temperatures fibers for artificial hair having a large elastic change in both the molding temperature region and the post-molding temperature region can be obtained.
- the viscoelasticity can also be adjusted by adjusting the fiber production conditions.
- viscoelasticity can be adjusted by appropriately changing the draft ratio and the draw ratio.
- the draft magnification is a magnification at which the resin exiting the nozzle hole is stretched until it is cooled
- the draw ratio is a magnification at which the undrawn yarn is stretched (a magnification at the time of stretching).
- the draft ratio and the draw ratio will be described in detail below.
- a composition containing a thermoplastic resin is heated and melted and discharged from a nozzle hole, and after passing through a heating cylinder as necessary, is cooled to obtain an undrawn yarn.
- a draft magnification is the magnification at which the yarn is cooled and undrawn after being discharged from the nozzle hole.
- the draw ratio can be calculated from the ratio of the undrawn yarn take-up speed to the discharge speed from the nozzle.
- the undrawn yarn is subjected to drawing treatment in order to improve the tensile strength of the fiber.
- the drawing process is a process of drawing the undrawn yarn once cooled while heating it at a temperature lower than the heating and melting temperature at the time of spinning, until the undrawn yarn (before heat drawing) is drawn.
- the draw ratio is the draw ratio.
- the stretch ratio in this case can be calculated by the ratio of the undrawn yarn unwinding speed and the yarn winding speed after the stretching treatment.
- thermoplastic resin is not particularly limited, and vinyl chloride resin, acrylic resin, polypropylene resin, polylactic acid resin, polyester resin, polyamide resin, or the like can be used. However, if only resin with low heat resistance such as vinyl chloride resin is used, the fiber will be thermally damaged in post molding at high temperature (180 ° C or higher), so heat resistant resin such as polyamide resin and polyester resin may be used alone or in combination. It is desirable to do.
- the present invention is particularly superior in terms of processability and strength, especially in the case of polyamide fibers mainly composed of polyamide resin and polyester fibers mainly composed of polyester resin.
- the polyamide fiber and the polyester fiber are preferably formed from a composition obtained by melt-kneading 100 parts by weight of a polyamide resin (or 100 parts by weight of a polyester resin) and 5 to 30 parts by weight of a phosphorus-based or bromine-based flame retardant. Fiber.
- flame retardancy is greatly improved by a combination of a resin and a predetermined proportion of a phosphorus-based or bromine-based flame retardant.
- the type of polyamide resin used for the polyamide-based fiber is not particularly limited.
- the polyamide resin is selected from the group consisting of nylon 6, nylon 6,6, nylon 4,6, nylon 12, nylon 6,10, and nylon 6,12. At least one resin is preferable, and nylon 6 and 6 are particularly preferable. When nylon 6 or 6 is used, the tactile feeling is particularly good.
- the weight average molecular weight (Mw) of the polyamide is, for example, any value within the range of 10,000 to 200,000, specifically 10,000, 20,000, 40,000, 60,000, 80,000, 100,000, There are 150,000 and 200,000.
- polyester resin used for the polyester fiber is not particularly limited, but there are polyethylene terephthalate, polyphenylene ether, polypropylene terephthalate, polybutylene terephthalate, etc. Among them, polyethylene terephthalate is most suitable in terms of heat resistance and the like. .
- the type of the phosphorus flame retardant is not particularly limited, and any phosphorus flame retardant that is generally used can be used. Specific examples include phosphate compounds, phosphonate compounds, phosphinate compounds, phosphine oxide compounds, phosphonite compounds, phosphinite compounds, phosphine compounds, and the like. These may be used alone or in combination of two or more.
- the brominated flame retardant is not particularly limited, and any brominated flame retardant that is generally used can be used. Specific examples include pentabromotoluene, hexabromobenzene, decabromodiphenyl, decabromodiphenyl ether, bis (tribromophenoxy) ethane, tetrabromophthalic anhydride, ethylenebis (tetrabromophthalimide), ethylenebis (pentabromophenyl), Bromine-containing phosphate ester flame retardants such as octabromotrimethylphenylindane and tris (tribromoneopentyl) phosphate, brominated polystyrene flame retardant, brominated polybenzyl acrylate flame retardant, brominated epoxy flame retardant, brominated Phenoxy flame retardant, brominated polycarbonate flame retardant, tetrabromobisphenol A, tetrabromobisphenol A-bis (2,3-dibro
- the content of the phosphorus-based or brominated flame retardant is such that the ratio with respect to 100 parts by weight of polyamide (or 100 parts by weight of the polyester resin) is 5 to 30 parts by weight, and is 5 to 20 parts by weight. Is more preferable. This is because, within such a range, deterioration of various physical properties can be avoided while ensuring sufficient flame retardancy.
- fine particles in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyamide resin (or 100 parts by weight of the polyester resin) may be contained.
- the ratio of the fine particles to 100 parts by weight of the polyamide resin (or 100 parts by weight of the polyester resin) is more preferably 0.2 to 3 parts by weight, and further preferably 0.2 to 2 parts by weight. This is because the above effect is particularly remarkable in such a ratio.
- the average particle size of the fine particles is preferably 0.1 to 15 ⁇ m, more preferably 0.2 to 10 ⁇ m, and further preferably 0.5 to 8 ⁇ m. This is because, within such a range, the effect of adjusting gloss and gloss is sufficiently large, and the fiber strength is not easily lowered by the addition of fine particles.
- the fine particles may be organic fine particles or inorganic fine particles, and may include both organic fine particles and inorganic fine particles.
- the organic fine particles only need to be at least partially incompatible with the polyamide resin or the polyester resin, and examples thereof include fine particles made of a crosslinked acrylic resin or a crosslinked polyester resin.
- the above-mentioned crosslinked acrylic particles can be obtained by water-dispersing an acrylic monomer and a crosslinking agent and crosslinking and curing.
- acrylic monomers used here include acrylic acid and derivatives of acrylic acid, such as methyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, hydroxyethyl acrylate, acrylonitrile, acrylamide, N -Methylolacrylamide; or methacrylic acid, methacrylic acid derivatives such as methyl methacrylate, butyl methacrylate, hexyl methacrylate, glycidyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, N-vinyl-2-pyrrolidone methacrylate, methacrylate
- vinyl monomers having one vinyl group in one molecule such as nitrile, methacrylamide, N-methylol methacrylamide, 2-hydroxy
- the above-mentioned crosslinked polyester particles can be obtained by dispersing an unsaturated polyester and a vinyl monomer in water, followed by crosslinking and curing.
- the unsaturated polyester used here is not particularly limited, and examples thereof include those obtained by polymerizing an ⁇ , ⁇ -unsaturated acid or a mixture thereof with a dihydric alcohol or a trihydric alcohol. Can do.
- Examples of the unsaturated acid include fumaric acid, maleic acid, itaconic acid, and examples of the saturated acid include phthalic acid, terephthalic acid, succinic acid, glutaric acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. It is done.
- dihydric alcohol and trihydric alcohol examples include ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, 1,3-propanediol, 1,6-hexanediol, and trimethylolpropane.
- the vinyl monomer is not particularly limited, and examples thereof include styrene, chlorostyrene, vinyl toluene, divinylbenzene, acrylic acid, methyl acrylate, acrylonitrile, ethyl acrylate, and diallyl phthalate.
- the cross-linking agent may be any monomer having two or more vinyl groups in one molecule, but one having two vinyl groups in one molecule is preferable.
- Preferred monomers for the crosslinking agent include, for example, divinylbenzene, reaction products of glycol and methacrylic acid or acrylic acid, such as ethylene glycol dimethacrylate and neopentyl glycol dimethacrylate, but are not limited thereto. is not.
- the addition amount of the crosslinking agent is preferably 0.02 to 5 parts by weight with respect to 100 parts by weight of the acrylic monomer.
- the polymerization initiator is preferably a peroxide radical polymerization initiator, and examples thereof include benzoyl peroxide, 2-ethylhexyl perbenzoate, di-tert-butyl peroxide, cumene hydroperoxide, and methyl ethyl ketone peroxide.
- the radical polymerization initiator is preferably used in an amount of 0.05 to 10 parts by weight with respect to 100 parts by weight of the acrylic monomer.
- the inorganic fine particles preferably have a refractive index close to the refractive index of the polyamide and / or phosphorus-containing flame retardant because of the influence on the transparency and color developability of the fiber.
- a refractive index close to the refractive index of the polyamide and / or phosphorus-containing flame retardant because of the influence on the transparency and color developability of the fiber.
- calcium carbonate, silicon oxide, oxidation Examples include titanium, aluminum oxide, zinc oxide, talc, kaolin, montmorillonite, bentonite, and mica.
- flame retardant aids In addition to the fine particles and flame retardants described above, flame retardant aids, heat-resistant agents, light stabilizers, fluorescent agents, antioxidants, antistatic agents, plasticizers, lubricants, resins other than thermoplastic resins, etc. Can be made. By containing a colorant such as a pigment, a pre-colored fiber (so-called original fiber) can be obtained.
- thermoplastic resin such as a polyamide resin or a polyester resin is dry-blended in advance with a desired ratio of the above-described additives such as a flame retardant or particles, and then melt-kneaded using a kneader.
- a kneader As an apparatus for melt kneading, various general kneaders can be used. Examples of the melt kneading include a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, and a kneader.
- a twin screw extruder is preferable from the viewpoint of adjusting the degree of kneading and ease of operation.
- the kneaded product obtained by melt kneading can be produced by melt spinning by a melt spinning method.
- melt spinning for example, melt spinning is performed at a temperature of 270 to 310 ° C. in a melt spinning apparatus such as an extruder, a gear pump, and a die, and the spun yarn is passed through a heating tube and then cooled to a glass transition point or lower.
- the spun yarn is obtained by taking up at a speed of 50 to 5000 m / min.
- the spun yarn may be cooled in a water tank containing cooling water to control the fineness.
- the temperature and length of the heating cylinder, the temperature and spray amount of the cold air tower, the temperature of the cooling water tank, the cooling time, and the take-up speed can be appropriately adjusted according to the discharge amount and the number of holes in the base.
- a spinning nozzle having a special nozzle hole shape can be used, and the cross-sectional shape of the fiber for artificial hair can be changed to irregular shapes such as a saddle type, a Y type, an H type, and an X type.
- the obtained undrawn yarn is subjected to a heat drawing treatment in order to improve the tensile strength of the fiber.
- the thermal drawing process is a two-step method in which an undrawn yarn is wound around a bobbin and then drawn in a step separate from the melt spinning step, or direct spinning in which the yarn is continuously drawn from the melt spinning step without being wound around the bobbin. Any method of stretching may be used. Further, the thermal stretching treatment is performed by a one-stage stretching method in which stretching is performed at a time to a target stretching ratio or a multi-stage stretching method in which stretching is performed to a target stretching ratio by two or more stretching.
- a heating means in the heat stretching treatment 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 fineness of the synthetic fiber is 30 to 80 dtex, preferably 35 to 75 dtex, which is suitable for artificial hair.
- the polyamide fiber is a non-crimped raw fiber, and the fineness is usually 10 to 100 dtex, more preferably 30 to 80 dtex, and further preferably 35 to 75 dtex.
- the manufactured synthetic fiber may be used as it is as a fiber for artificial hair as it is, but it is also possible to improve the tactile sensation and the like by applying a treatment agent containing an oil such as silicone.
- the treatment agent may be applied before, during, or after processing the synthetic fiber into a hair product. More suitable in terms of etc.
- the artificial hair fiber may be used alone for a hair product (head ornament product), or may be used by mixing human hair or other artificial hair.
- the hair products are wigs, hair pieces, blades, extension hairs, doll hairs, etc., and the use of the fiber for artificial hair is not particularly limited. In addition to hair products, it can also be used for false eyelashes, false eyelashes, false eyebrows and the like.
- the polyamide fiber (or polyester fiber) was produced by the following method. First, the polyamide resin (or polyester resin), phosphorus-based or brominated flame retardant, and fine particles as raw materials were each dried so that the water content contained was 100 ppm or less.
- Nylon 6 Ube Industries, Ltd. 1013B Nylon 6, 6: Toray Industries, Inc., CM3001-N Phosphorus flame retardant: Daihachi Chemical Industry Co., Ltd., PX-200 Brominated flame retardant: Albemarle Japan, HP-7010 Fine particles: Cross-linked acrylic particles, average particle size 1.8 ⁇ m, Soken Chemical Co., Ltd. Polyester (PET): Mitsubishi Chemical Corporation, BK-2180
- the blending (mass ratio) of the raw materials is shown in Table 1 below.
- a predetermined amount of coloring pellets was added to the dried raw material, and dry blended with each mixing species and mixing ratio shown in Table 1.
- the dry blend was melt kneaded at a temperature of 280 ° C. And the kneaded material was shape
- the pellet molded body was dried so that the water content contained was 100 ppm or less, and then molded into an undrawn yarn by a melt spinning machine. More specifically, as the nozzle of the spinneret in the melt spinning machine, a hole having a circular cross section and a nozzle hole diameter of 0.5 mm was used. With this melt spinning machine, the molten polymer of the pellet molded body was discharged from the nozzle hole in a state where the temperature was 280 ° C. The discharged molten polymer was cooled in a 50 ° C. water bath layer located 30 mm below the die and wound up. In this way, an undrawn yarn was obtained. The draft ratio was adjusted by changing the winding speed of the undrawn yarn.
- the obtained unstretched yarn was stretched 4 times and then heat-treated.
- the fiber comprised mainly by polyamide (or polyester) was obtained by winding at the speed
- heat rolls heated to 85 ° C. and 200 ° C. were used.
- fibers according to Examples 1 to 4 and Comparative Examples 1 to 2 were obtained.
- the draw ratio was adjusted by changing the unwinding speed of the undrawn yarn.
- oven curl properties 2 g of a fiber bundle obtained by bundling fibers having a length of 50 cm was wound around an aluminum cylinder of 20 mm ⁇ , and both ends were fixed, put into an air circulation oven at 100 ° C., and heated for 30 minutes. Next, the aluminum tube (with the fiber wound) was left in a temperature-controlled room at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours. Thereafter, the fiber bundle was removed from the stainless steel tube, and one end was fixed and suspended. The length from the root to the tip was evaluated by the value divided by the total length (50 cm) before curling. The smaller the value, the more curled. The evaluation is based on the following criteria, and excellent and good are acceptable values. Excellent value is less than 0.75 Good value is 0.75 or more and less than 0.85 Defective value is 0.85 or more
- Dynamic viscoelasticity (extension elastic modulus) was measured under the measurement conditions of a frequency of 1.0 Hz, a start temperature of 30 ° C., an end temperature of 260 ° C., and a temperature increase rate of 2 ° C./min.
- the measuring instrument used was DMS6100 manufactured by SII Nano Technology.
- the fiber was measured by setting a distance between chucks of 3 mm and sandwiching a bundle of 40 fibers.
- the ratio (draft ratio / draw ratio) relative stretch ratio D 2 of the draft ratio D 1, and 1.5 to 14.0 ratio of the storage modulus (E '90 / E' 150 ) were 3 to 20
- Examples 1 to 4 were excellent not only in oven curl properties and processability, but also in strength.
- Examples 1 and 4 having a storage elastic modulus ratio (E ′ 90 / E ′ 150 ) of 4 to 10 gave particularly good results in oven curl properties.
- the ratio (D 1 / D 2 ) of the draft ratio D 1 to the draw ratio D 2 is less than 1.5, the undrawn yarn is stretched too much at the time of drawing, and the yarn tends to break, so that the workability tends to deteriorate. become.
- Example 5 there against stretching ratio D 2 of the draft ratio D 1 even ratio (D 1 / D 2) is 1.5, the ratio of drawing ratio D 2 of the draft ratio D 1 (D 1 / D 2 ) Is in the range of good workability even at 1.5, and has a usable range of characteristics.
- the ratio of storage elastic modulus (E ′ 90 / E ′ 150 ) was 18.5, and the oven curl property and physical properties (tensile strength) were not good but good. It has a range of characteristics that can be used.
- Example 6 there ratio stretching ratio D 2 of the draft ratio D 1 (D 1 / D 2 ) is also 12, the ratio of drawing ratio D 2 of the draft ratio D 1 (D 1 / D 2 ) is No. 12 also has a tensile strength (physical property) in a good range and has a usable characteristic.
- Comparative Example 1 having a storage elastic modulus ratio (E ′ 90 / E ′ 150 ) of less than 3 is inferior in oven curl property, and the storage elastic modulus ratio (E ′ 90 / E ′ 150 ) is 20.
- the strength was not only poor in oven curl but also in strength.
- the measurement result of the dynamic viscoelasticity of Example 1 is shown in FIG. 2, and the measurement result of the dynamic viscoelasticity of Comparative Example 1 is shown in FIG.
- FIG. 3 it was confirmed that the artificial hair fiber of Comparative Example 1 did not melt even at a high temperature of 240 ° C., retained the storage elastic modulus E ′, and had very high heat resistance. Is too high, the melt does not melt not only in the molding temperature region (90 to 150 ° C.) but also in the post-molding temperature region (180 to 240 ° C.), and the changes in storage elastic modulus E ′ and loss elastic modulus E ′′ are small. On the other hand, it was confirmed that the artificial hair fiber of Example 1 has a large rate of change in both the molding temperature region and the post-molding temperature region, and the moldability is very high.
- the storage modulus E with respect to the temperature at a constant, indicates the tangent crystalline state through the region (glass state region) of the glassy state, the code M 2 in FIG. at a high temperature side of the glass state region, the rate of change indicates a tangent line passing through the transition region becomes maximum.
- the crystal state collapses and melting starts.
- the artificial hair fiber of Example 1 has a temperature coordinate of the intersection point P in the range of 180 to 240 ° C.
- the use of the fiber for artificial hair according to the present invention is not particularly limited, and can be used for various hair products such as wigs, hairpieces, blades, hair extensions such as extension hairs, or doll hairs. .
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Abstract
Description
前記温度に対する貯蔵弾性率E’の曲線は、該貯蔵弾性率E’が一定のガラス状態領域と、該ガラス状態領域よりも高温で、変化率が最大となる転移領域とを有する。この貯蔵弾性率E’の曲線に対する、ガラス状態領域を通る接線と転移領域を通る接線とが交差する交点の温度座標が、180~240℃に位置するものが、より本発明に適している。
人工毛髪繊維は、ポリエステル樹脂と、ポリアミド樹脂の何れか一方又は両方の熱可塑性樹脂を主成分とする樹脂組成物から製造されたものがより好ましい。
また、前記樹脂組成物を、ノズル孔から溶融吐出して未延伸糸を製造した後、前記未延伸糸を延伸処理して製造された人工毛髪用繊維であって、溶融吐出から未延伸糸を製造する間に引き伸ばされた倍率D1と、延伸処理の間に引き伸ばされた倍率D2との比D1/D2が、1.5~14.0になるものがより好ましい。
上記人工毛髪用繊維を用いて頭髪製品を製造することもできる。 The present invention is to provide a product using the fiber for artificial hair and the artificial hair fibers, storage modulus at 90 and 0.99 ° C. 'storage modulus E at 90 ° C. in a' storage modulus E with respect to temperature 90 / E '0.99' ratio E of 0.99 'E is 3 to 20 fiber for artificial hair.
The curve of the storage elastic modulus E ′ with respect to the temperature has a glass state region where the storage elastic modulus E ′ is constant and a transition region where the rate of change is maximum at a higher temperature than the glass state region. It is more suitable for the present invention that the temperature coordinate of the intersection point where the tangent line passing through the glass state region and the tangent line passing through the transition region intersect with the storage elastic modulus E ′ curve is 180 to 240 ° C.
The artificial hair fiber is more preferably produced from a resin composition containing as a main component either one or both of a polyester resin and a polyamide resin.
The resin composition is a fiber for artificial hair produced by melt-discharging the resin composition from a nozzle hole to produce an unstretched yarn, and then stretching the unstretched yarn. It is more preferable that the ratio D 1 / D 2 between the magnification D 1 stretched during the production and the magnification D 2 stretched during the stretching process is 1.5 to 14.0.
A hair product can also be produced using the artificial hair fibers.
E’90/E’150が3未満であると、成形温度領域(90~150℃)での弾性率の変化が小さいため、カールの成形が困難であり、カール性が不良となる。一方、E’90/E’150が20を超えると、繊維が収縮してしまうことから、カール性が不良となる。また、E’90/E’150が4~10の場合、繊維が収縮せずに優れたカール性を実現できることから、特に好ましい。 The larger the change in the elastic modulus, the better the curling property, but the too large change means shrinkage of the fiber. For example, temperature (° C.) 90 / E '150' ratio E of 150 '90 and 150 ° C. storage modulus E at' the storage modulus E at 90 ° C. in 'the storage modulus E with respect is 3-20 More preferably, it is 4 to 10.
When E ′ 90 / E ′ 150 is less than 3, the change in elastic modulus in the molding temperature region (90 to 150 ° C.) is small, so that curling is difficult and curling properties are poor. On the other hand, if E ′ 90 / E ′ 150 exceeds 20, the fiber contracts, resulting in poor curling properties. Further, when E ′ 90 / E ′ 150 is 4 to 10, it is particularly preferable because excellent curling properties can be realized without shrinking the fibers.
樹脂組成物は、熱可塑性樹脂を主成分(含有量50質量%以上)とし、必要に応じて難燃剤、充填剤、着色剤、老化防止剤等の添加剤を含むものである。粘弾性(E’、E”等)は、例えば、2種類以上の熱可塑性樹脂の配合比率、又は熱可塑性樹脂と添加剤(難燃剤、フィラー等)の配合比率により調整することができる。特に、ガラス転移温度の異なる熱可塑性樹脂を2種類以上配合することで、成形温度領域と後成形温度領域の両方で弾性変化の大きい人工毛髪用繊維を得ることができる。 <Resin composition>
The resin composition contains a thermoplastic resin as a main component (content of 50% by mass or more) and contains additives such as a flame retardant, a filler, a colorant, and an anti-aging agent as necessary. Viscoelasticity (E ′, E ″, etc.) can be adjusted by, for example, the blending ratio of two or more thermoplastic resins or the blending ratio of the thermoplastic resin and additives (flame retardant, filler, etc.). By blending two or more thermoplastic resins having different glass transition temperatures, fibers for artificial hair having a large elastic change in both the molding temperature region and the post-molding temperature region can be obtained.
熱可塑性樹脂は特に限定されず、塩化ビニル樹脂、アクリル樹脂、ポリプロピレン樹脂、ポリ乳酸樹脂、ポリエステル樹脂、ポリアミド樹脂等を用いることができる。しかし、塩化ビニル樹脂等、耐熱性が低い樹脂だけを用いると、高温(180℃以上)の後成形で、繊維が熱損傷するので、ポリアミド樹脂、ポリエステル樹脂等の耐熱性の樹脂を単独もしくは併用することが望ましい。 <Thermoplastic resin>
The thermoplastic resin is not particularly limited, and vinyl chloride resin, acrylic resin, polypropylene resin, polylactic acid resin, polyester resin, polyamide resin, or the like can be used. However, if only resin with low heat resistance such as vinyl chloride resin is used, the fiber will be thermally damaged in post molding at high temperature (180 ° C or higher), so heat resistant resin such as polyamide resin and polyester resin may be used alone or in combination. It is desirable to do.
以下に、合成繊維の製造工程の一例を説明するが、本発明はこれに限定されるものではない。
ポリアミド樹脂、ポリエステル樹脂などの熱可塑性樹脂に、上述した難燃剤や粒子等の添加剤を所望の割合で事前にドライブレンドした後、混練機を用いて溶融混練する。溶融混練するための装置としては、種々の一般的な混練機を用いることができる。溶融混練としては、たとえば一軸押出機、二軸押出機、ロール、バンバリーミキサー、ニーダーなどが挙げられる。これらのうちでは、二軸押出機が、混練度の調整、操作の簡便性の点から好ましい。溶融混練によって得られた混練物を溶融紡糸法によって溶融紡糸することによって製造することができる。 <Manufacturing process>
Although an example of the synthetic fiber manufacturing process will be described below, the present invention is not limited to this.
A thermoplastic resin such as a polyamide resin or a polyester resin is dry-blended in advance with a desired ratio of the above-described additives such as a flame retardant or particles, and then melt-kneaded using a kneader. As an apparatus for melt kneading, various general kneaders can be used. Examples of the melt kneading include 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. The kneaded product obtained by melt kneading can be produced by melt spinning by a melt spinning method.
製造された合成繊維は、そのまま人工毛髪用繊維として用いてもよいが、シリコーン等の油剤を含む処理剤を塗布し、触感等を改良することもできる。処理剤の塗布は、合成繊維を頭髪製品に加工する前、加工する途中、又は加工後の何れの段階で行ってもよいが、頭髪製品へ加工する途中の塗布が、作業性、均一塗布性等の点でより適している。 <Post-processing>
The manufactured synthetic fiber may be used as it is as a fiber for artificial hair as it is, but it is also possible to improve the tactile sensation and the like by applying a treatment agent containing an oil such as silicone. The treatment agent may be applied before, during, or after processing the synthetic fiber into a hair product. More suitable in terms of etc.
以下、実施例にかかる毛髪用繊維束の製造方法について説明する。ポリアミド系繊維(又はポリエステル系繊維)は、以下の方法で製造した。先ず、含有する水分量が100ppm以下となるように、原料としてのポリアミド樹脂(又はポリエステル樹脂)、リン系又は臭素系難燃剤、及び微粒子をそれぞれ乾燥させた。 <Manufacturing process>
Hereinafter, the manufacturing method of the fiber bundle for hair concerning an Example is demonstrated. The polyamide fiber (or polyester fiber) was produced by the following method. First, the polyamide resin (or polyester resin), phosphorus-based or brominated flame retardant, and fine particles as raw materials were each dried so that the water content contained was 100 ppm or less.
ナイロン6:宇部興産株式会社、1013B
ナイロン6,6:東レ株式会社、CM3001‐N
リン系難燃剤:大八化学工業株式会社、PX-200
臭素系難燃剤:アルベマール日本株式会社、HP-7010
微粒子:架橋アクリル粒子、平均粒子径1.8μm、綜研化学株式会社
ポリエステル(PET):三菱化学株式会社、BK‐2180 The following were used as raw materials.
Nylon 6: Ube Industries, Ltd. 1013B
Nylon 6, 6: Toray Industries, Inc., CM3001-N
Phosphorus flame retardant: Daihachi Chemical Industry Co., Ltd., PX-200
Brominated flame retardant: Albemarle Japan, HP-7010
Fine particles: Cross-linked acrylic particles, average particle size 1.8 μm, Soken Chemical Co., Ltd. Polyester (PET): Mitsubishi Chemical Corporation, BK-2180
オーブンカール性は、長さ50cmの繊維を束ねた繊維束2グラムを、20mmφのアルミ製筒に巻き付け乍ら両端を固定し、100℃の空気循環式オーブンに投入して30分間加熱した。次いで、アルミ筒(繊維を巻き付けたままで)を温度23℃、相対湿度50%の恒温室に24時間放置した。その後、ステンレス筒から繊維束を取り外し、一方の端を固定して吊り下げた。その根元から先端までの長さを、カール前の全長(50cm)で割った値で評価した。値が小さいほどカールがかかっている。評価は、以下の基準であり、優良と良が合格値である。
優良 値が0.75未満
良 値が0.75以上0.85未満
不良 値が0.85以上 <Oven curl properties>
For the oven curl property, 2 g of a fiber bundle obtained by bundling fibers having a length of 50 cm was wound around an aluminum cylinder of 20 mmφ, and both ends were fixed, put into an air circulation oven at 100 ° C., and heated for 30 minutes. Next, the aluminum tube (with the fiber wound) was left in a temperature-controlled room at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours. Thereafter, the fiber bundle was removed from the stainless steel tube, and one end was fixed and suspended. The length from the root to the tip was evaluated by the value divided by the total length (50 cm) before curling. The smaller the value, the more curled. The evaluation is based on the following criteria, and excellent and good are acceptable values.
Excellent value is less than 0.75 Good value is 0.75 or more and less than 0.85 Defective value is 0.85 or more
加工性は、繊維の製造工程(紡糸、延伸)における糸切れの頻度を調べ、以下の基準で評価した。優良と良が合格値である。
優良 糸切れなし
良 30分に1回程度の糸切れはあるが、製品の品質上問題なし
不良 糸切れが多く製造困難 <Processability>
The processability was evaluated according to the following criteria by examining the frequency of yarn breakage in the fiber manufacturing process (spinning, drawing). Excellent and good are acceptable values.
Excellent No thread breakage Good Good There is a thread breakage once every 30 minutes, but there is no problem with the quality of the product.
JIS-L1069に準拠して10本の繊維をランダムに選択して引張試験を行い、平均値を求めた。試験温度は23℃、相対湿度は50%、引張速度は200mm/min、空間距離(チャック間距離)は200mmで行った。引張強度(cN/dtex)が1.0以上2.0以下のものを優良、引張強度(cN/dtex)が0.5以上3.0以下のものを良、引張強度(cN/dtex)が0.5未満、又は、3.0を超えるものを不良とした。 <Physical properties>
Ten fibers were randomly selected according to JIS-L1069 and subjected to a tensile test to obtain an average value. The test temperature was 23 ° C., the relative humidity was 50%, the tensile speed was 200 mm / min, and the spatial distance (distance between chucks) was 200 mm. Excellent tensile strength (cN / dtex) of 1.0 to 2.0, excellent tensile strength (cN / dtex) of 0.5 to 3.0, tensile strength (cN / dtex) Those less than 0.5 or more than 3.0 were regarded as defective.
周波数1.0Hz、開始温度30℃、終了温度260℃、昇温速度2℃/分の測定条件で、動的粘弾性(伸張弾性率)を測定した。測定機器はエスアイアイ・ナノテクノロジー社製のDMS6100を用いた。なお、繊維は、チャック間距離を3mmとし、40本の繊維を並べた束を挟んで測定した。 <Dynamic viscoelasticity>
Dynamic viscoelasticity (extension elastic modulus) was measured under the measurement conditions of a frequency of 1.0 Hz, a start temperature of 30 ° C., an end temperature of 260 ° C., and a temperature increase rate of 2 ° C./min. The measuring instrument used was DMS6100 manufactured by SII Nano Technology. The fiber was measured by setting a distance between chucks of 3 mm and sandwiching a bundle of 40 fibers.
ドラフト倍率D1の延伸倍率D2に対する比(D1/D2)が1.5未満であると、延伸時に未延伸糸を引き伸ばし過ぎて糸が切れやすくなることから、加工性が悪化する傾向になる。一方、ドラフト倍率D1の延伸倍率D2に対する比(D1/D2)が14.0を超えると、延伸処理(未延伸糸の引き伸ばし)が十分に行われないことから、引張強度は小さくなる傾向になる。
実施例5では、貯蔵弾性率の比(E’90/E’150)が3.6であり、オーブンカール性及び加工性は優良ではなく良であったが、この範囲でも十分に使用可能な範囲の特性を有している。また、実施例5は、ドラフト倍率D1の延伸倍率D2に対する比(D1/D2)が1.5でもあり、このドラフト倍率D1の延伸倍率D2に対する比(D1/D2)が1.5においても加工性が良の範囲であり、使用可能な範囲の特性を有している。
実施例6では、貯蔵弾性率の比(E’90/E’150)が18.5であり、オーブンカール性及び物性(引張強度)は優良ではなく良であったが、この範囲でも十分に使用可能な範囲の特性を有している。また、実施例6は、ドラフト倍率D1の延伸倍率D2に対する比(D1/D2)が12でもあり、このドラフト倍率D1の延伸倍率D2に対する比(D1/D2)が12においても引張強度(物性)が良の範囲であり、使用可能な範囲の特性を有している。 The ratio (draft ratio / draw ratio) relative stretch ratio D 2 of the draft ratio D 1, and 1.5 to 14.0 ratio of the storage modulus (E '90 / E' 150 ) were 3 to 20 Examples 1 to 4 were excellent not only in oven curl properties and processability, but also in strength. Among these, Examples 1 and 4 having a storage elastic modulus ratio (E ′ 90 / E ′ 150 ) of 4 to 10 gave particularly good results in oven curl properties.
When the ratio (D 1 / D 2 ) of the draft ratio D 1 to the draw ratio D 2 is less than 1.5, the undrawn yarn is stretched too much at the time of drawing, and the yarn tends to break, so that the workability tends to deteriorate. become. On the other hand, if the ratio (D 1 / D 2 ) of the draft ratio D 1 to the draw ratio D 2 exceeds 14.0, the drawing process (drawing of the undrawn yarn) is not sufficiently performed, so the tensile strength is small. Tend to be.
In Example 5, the ratio of storage elastic modulus (E ′ 90 / E ′ 150 ) was 3.6, and the oven curl property and workability were not good but good, but this range can also be used sufficiently. Has a range of characteristics. In Example 5, there against stretching ratio D 2 of the draft ratio D 1 even ratio (D 1 / D 2) is 1.5, the ratio of drawing ratio D 2 of the draft ratio D 1 (D 1 / D 2 ) Is in the range of good workability even at 1.5, and has a usable range of characteristics.
In Example 6, the ratio of storage elastic modulus (E ′ 90 / E ′ 150 ) was 18.5, and the oven curl property and physical properties (tensile strength) were not good but good. It has a range of characteristics that can be used. In Example 6, there ratio stretching ratio D 2 of the draft ratio D 1 (D 1 / D 2 ) is also 12, the ratio of drawing ratio D 2 of the draft ratio D 1 (D 1 / D 2 ) is No. 12 also has a tensile strength (physical property) in a good range and has a usable characteristic.
The use of the fiber for artificial hair according to the present invention is not particularly limited, and can be used for various hair products such as wigs, hairpieces, blades, hair extensions such as extension hairs, or doll hairs. .
Claims (5)
- 温度に対する貯蔵弾性率E’において90℃での貯蔵弾性率E’90と150℃での貯蔵弾性率E’150との比E’90/E’150が3~20である人工毛髪用繊維。 90 / E '150 3-20 a is artificial hair fibers' ratio E of the 150' the storage modulus E at 90 and 150 ° C. 'storage modulus E at 90 ° C. in a' storage modulus E with respect to temperature.
- 前記温度に対する貯蔵弾性率E’の曲線は、該貯蔵弾性率E’が一定のガラス状態領域と、該ガラス状態領域よりも高温で、変化率が最大となる転移領域とを有し、
前記貯蔵弾性率E’の曲線に対する、前記ガラス状態領域を通る接線と前記転移領域を通る接線とが交差する交点の温度座標が、180~240℃に位置する請求項1記載の人工毛髪用繊維。 The curve of the storage elastic modulus E ′ with respect to the temperature has a glass state region where the storage elastic modulus E ′ is constant, and a transition region where the rate of change is maximum at a higher temperature than the glass state region,
The fiber for artificial hair according to claim 1, wherein a temperature coordinate of an intersection point of a tangent line passing through the glass state region and a tangent line passing through the transition region with respect to the curve of the storage elastic modulus E 'is located at 180 to 240 ° C. . - ポリエステル樹脂と、ポリアミド樹脂の何れか一方又は両方の熱可塑性樹脂を主成分とする樹脂組成物から製造された請求項1又は請求項2記載の人工毛髪用繊維。 The fiber for artificial hair according to claim 1 or 2, wherein the fiber is produced from a resin composition comprising as a main component a thermoplastic resin of either one or both of a polyester resin and a polyamide resin.
- 前記樹脂組成物を、ノズル孔から溶融吐出して未延伸糸を製造した後、前記未延伸糸を延伸処理して製造された人工毛髪用繊維であって、
溶融吐出から未延伸糸を製造する間に引き伸ばされた倍率D1と、延伸処理の間に引き伸ばされた倍率D2との比D1/D2が、1.5~14.0である請求項3記載の人工毛髪用繊維。 A fiber for artificial hair produced by melting and discharging the resin composition from a nozzle hole to produce an unstretched yarn, and then stretching the unstretched yarn,
The ratio D 1 / D 2 of the magnification D 1 stretched during the production of undrawn yarn from melt discharge and the magnification D 2 stretched during the stretching treatment is 1.5 to 14.0. Item 5. An artificial hair fiber according to Item 3. - 請求項1乃至請求項4の何れか1項記載の人工毛髪用繊維を用いた頭髪製品。
A hair product using the artificial hair fiber according to any one of claims 1 to 4.
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JP2013515121A JP5914469B2 (en) | 2011-05-13 | 2012-05-11 | Artificial hair fibers and hair products |
CN201280021528.6A CN103501647A (en) | 2011-05-13 | 2012-05-11 | Fiber for artificial hair, and hairpiece product |
SG2013080262A SG194688A1 (en) | 2011-05-13 | 2012-05-11 | Artificial hair fiber and hairpiece product |
KR1020137029611A KR101907049B1 (en) | 2011-05-13 | 2012-05-11 | Fiber for artificial hair, and hairpiece product |
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JP2005042234A (en) * | 2003-07-25 | 2005-02-17 | Kaneka Corp | Flame-retardant polyester-based fiber for artificial hair |
JP2005076147A (en) * | 2003-09-01 | 2005-03-24 | Kaneka Corp | Flame-retardant polyester fiber for artificial hair |
KR101035603B1 (en) * | 2003-12-08 | 2011-05-19 | 가부시키가이샤 가네카 | Flame-retardant polyester fiber for artificial hair and manufacturing method thereof |
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WO2007049561A1 (en) * | 2005-10-28 | 2007-05-03 | Kaneka Corporation | Polyester-based artificial hair |
CN102170800B (en) * | 2008-09-30 | 2013-11-13 | 株式会社钟化 | Hair extension, hair accessory using same and method for producing hair extension |
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2012
- 2012-05-11 WO PCT/JP2012/062133 patent/WO2012157561A1/en active Application Filing
- 2012-05-11 CN CN201280021528.6A patent/CN103501647A/en active Pending
- 2012-05-11 KR KR1020137029611A patent/KR101907049B1/en active IP Right Grant
- 2012-05-11 SG SG2013080262A patent/SG194688A1/en unknown
- 2012-05-11 AP AP2013007287A patent/AP2013007287A0/en unknown
- 2012-05-11 US US14/114,539 patent/US20140109924A1/en not_active Abandoned
- 2012-05-11 JP JP2013515121A patent/JP5914469B2/en active Active
-
2013
- 2013-11-11 ZA ZA2013/08463A patent/ZA201308463B/en unknown
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JP2009167571A (en) * | 2008-01-18 | 2009-07-30 | Kaneka Corp | Polyimide fiber assembly and use thereof, and method for producing the polyimide fiber assembly |
JP2009235626A (en) * | 2008-03-27 | 2009-10-15 | Kaneka Corp | Flame-retardant polyester-based artificial hair |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170260391A1 (en) * | 2014-12-09 | 2017-09-14 | Denka Company Limited | Polyamide-based fiber for artificial hair having exceptional dripping resistance upon combustion |
JPWO2016092922A1 (en) * | 2014-12-09 | 2017-09-21 | デンカ株式会社 | Polyamide-based artificial hair fibers with excellent drip resistance during combustion |
US10477908B2 (en) | 2015-03-30 | 2019-11-19 | Kaneka Corporation | Acrylic fiber for artificial hair, method for producing same, and head decoration product comprising same |
US10433605B2 (en) | 2015-06-26 | 2019-10-08 | Kaneka Corporation | Acrylic fiber for artificial hair, manufacturing method therefor and head accessory containing same |
WO2021024603A1 (en) * | 2019-08-02 | 2021-02-11 | 株式会社アデランス | Method for manufacturing wig false hair and wig |
JP2021025147A (en) * | 2019-08-02 | 2021-02-22 | 株式会社アデランス | Method of manufacturing wig imitation hair and wig |
Also Published As
Publication number | Publication date |
---|---|
KR20140022410A (en) | 2014-02-24 |
JP5914469B2 (en) | 2016-05-11 |
KR101907049B1 (en) | 2018-10-11 |
SG194688A1 (en) | 2013-12-30 |
US20140109924A1 (en) | 2014-04-24 |
AP2013007287A0 (en) | 2013-12-31 |
JPWO2012157561A1 (en) | 2014-07-31 |
CN103501647A (en) | 2014-01-08 |
ZA201308463B (en) | 2015-01-28 |
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