WO2017187843A1 - 人工毛髪繊維 - Google Patents
人工毛髪繊維 Download PDFInfo
- Publication number
- WO2017187843A1 WO2017187843A1 PCT/JP2017/011202 JP2017011202W WO2017187843A1 WO 2017187843 A1 WO2017187843 A1 WO 2017187843A1 JP 2017011202 W JP2017011202 W JP 2017011202W WO 2017187843 A1 WO2017187843 A1 WO 2017187843A1
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- WO
- WIPO (PCT)
- Prior art keywords
- core
- sheath
- resin composition
- brominated
- artificial hair
- Prior art date
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Classifications
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41G—ARTIFICIAL FLOWERS; WIGS; MASKS; FEATHERS
- A41G3/00—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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
Definitions
- the present invention relates to fibers (hereinafter simply referred to as “artificial hair fibers”) used for artificial hair such as wigs, hair wigs, and false hairs that can be attached to and detached from the head.
- artificial hair fibers used for artificial hair such as wigs, hair wigs, and false hairs that can be attached to and detached from the head.
- Patent Document 1 proposes vinyl chloride as a material constituting artificial hair fibers. This is because the processability and low cost of vinyl chloride in artificial hair fibers are excellent.
- the artificial hair fiber made of vinyl chloride has a glass transition temperature of vinyl chloride near 80 ° C, and therefore has poor heat resistance against hair irons, etc.
- the fibers may be fused or twisted. As a result, the fibers may be damaged or cut.
- Patent Document 2 describes an artificial hair fiber made of polyester, and has improved heat resistance against a hair iron.
- the artificial hair fiber made of polyester has a problem that the touch is harder than the PVC fiber.
- Patent Document 3 describes an artificial hair fiber with improved tactile sensation using polyamide as a raw material.
- the elastic modulus is lowered, and the initial state after curling is performed. There was a problem that curl retention deteriorated with time.
- Patent Document 4 describes an artificial hair fiber having a core-sheath structure composed of polyester in the core and polyamide in the sheath. To some extent has been solved.
- Patent Document 4 has a problem that the core part and the sheath part may be easily peeled off.
- the present invention has been made in view of such circumstances, has improved the problem of peeling between the core and the sheath, has a good tactile sensation similar to human hair, and has excellent curl retention. It provides hair fibers.
- the inventors of the present invention have examined the cause of the peeling between the core and the sheath.
- the difference in melt viscosity between the polyester in the core and the polyamide in the sheath is large, the orientation is due to the difference in how stress is applied during stretching.
- there is a difference in the degree and as a result, there is a difference in the shrinkage between the core and the sheath, and if the core and sheath are peeled off when curled with a gear oven or a hair iron, etc. I noticed that there is.
- the said subject was solved by making the fiber for artificial hair the following structures, and came to completion of this invention.
- An artificial hair fiber having a core-sheath structure comprising a core part and a sheath part covering the core part, wherein the core part is made of a core resin composition containing polyester, and the sheath part contains polyamide.
- a sheath resin composition wherein the core and the sheath have a core / sheath mass ratio of 40/60 to 90/10, and the melt viscosity a of the polyester of the core resin composition and the sheath resin
- the core resin composition comprises brominated benzyl acrylate, brominated phenol, polydibromophenylene oxide, brominated polystyrene, ethylene bistetrabromophthalimide, bis (pentabromophenyl) ethane, brominated epoxy, brominated phenoxy.
- the artificial hair fiber according to (1) which contains at least one brominated flame retardant selected from the group consisting of a brominated polycarbonate and a bromine-containing triazine compound.
- the sheath resin composition comprises brominated benzyl acrylate, brominated phenol, polydibromophenylene oxide, brominated polystyrene, ethylene bistetrabromophthalimide, bis (pentabromophenyl) ethane, brominated epoxy, brominated phenoxy.
- the artificial hair fiber according to (1) or (2) which contains at least one brominated flame retardant selected from the group consisting of a brominated polycarbonate and a bromine-containing triazine compound.
- the sheath resin composition contains 0.5 to 3 parts by mass of a compatibilizing agent with respect to 100 parts by mass of the polyamide, according to any one of (1) to (6).
- the polyester of the core resin composition is made of polyethylene terephthalate and polybutylene terephthalate, and the mass ratio of the polyethylene terephthalate and polybutylene terephthalate is 40/60 to 90/10 (1)
- the polyester of the core resin composition is made of polyethylene terephthalate and polypropylene terephthalate, and the mass ratio of the polyethylene terephthalate and polytrimethylene terephthalate is 40/60 to 90/10 (1 )-(7)
- the polyamide of the sheath resin composition is made of nylon 6,6 and nylon 6, and the mass ratio of the nylon 6,6 and nylon 6 is 70/30 to 95/5 ( The artificial hair fiber according to any one of 1) to (9).
- ADVANTAGE OF THE INVENTION According to this invention, it can prevent that a core part and a sheath part peel and can provide the artificial hair fiber which has favorable tactile sensation similar to human hair, and was excellent in curl retention property.
- the artificial hair fiber of the present invention is an artificial hair fiber having a core-sheath structure comprising a core part and a sheath part covering the core part, and the core part is made of a core resin composition containing polyester.
- the sheath part is made of a sheath resin composition containing polyamide, and the core / sheath part has a core / sheath mass ratio of 40/60 to 90/10, and the core resin composition has a polyester composition.
- the viscosity ratio a / b of the melt viscosity a and the melt viscosity b of the polyamide of the sheath resin composition is 0.5 to 2.5, and appropriately contains a brominated flame retardant and a compatibilizer.
- the core / sheath mass ratio between the core and the sheath is 40/60 to 90/10, preferably 50/50 to 85/15.
- the mass ratio of the core / sheath is less than 40/60, the polyamide in the sheath absorbs moisture in the atmosphere, and the elastic modulus decreases. Retention is worse.
- the ratio exceeds 90/10 the polyamide layer in the sheath is thin, and a good tactile sensation similar to human hair cannot be obtained.
- melt viscosity The melt viscosity of polyester or polyamide is dehumidified and dried so that the water absorption of the polyester pellets or polyamide pellets is 100 ppm or less, the sample amount is 20 cc, the set temperature is 285 ° C., the piston speed is 200 mm / min, and the capillary length is 20 mm. The value measured under the condition of a capillary diameter of 1 mm. As the measuring instrument, a melt viscosity was used with a Capillograph 1D manufactured by Toyo Seiki Seisakusho.
- the viscosity ratio a / b of the melt viscosity a of the polyester at the core and the melt viscosity b of the polyamide at the sheath is 0.5 to 2.5, preferably 0.8 to 2.2.
- the viscosity ratio is less than 0.5, the melt viscosity of the core is low at the time of spinning, which causes a problem that yarn breakage occurs at the time of spinning or the core portion and the sheath portion are easily peeled off.
- the viscosity ratio exceeds 2.5, the problem of the core part and the sheath part occurs.
- Core part A core part consists of a core part resin composition containing polyester.
- the type of polyester is not particularly limited, but is preferably at least one resin selected from polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate.
- the polyester a resin in which polyethylene terephthalate and polybutylene terephthalate are mixed can be used, and the mass ratio is preferably 40/60 to 90/10, and more preferably 50/50 to 70/30.
- the mass ratio of the polyethylene terephthalate in the core is less than 40/60, the heat resistance tends to be low, and when it exceeds 90/10, the effect of improving the tactile sensation cannot be obtained.
- the polyester a resin in which polyethylene terephthalate and polytrimethylene terephthalate are mixed can be used, and the mass ratio is preferably 40/60 to 90/10, and more preferably 50/50 to 70/30.
- the mass ratio of polyethylene terephthalate in the core is less than 40/60, the heat resistance tends to be low, and when it exceeds 90/10, the effect of improving the tactile sensation cannot be obtained.
- the core resin composition preferably contains only polyester as a resin component, but may contain another resin.
- the mass ratio of polyester / all resin components in the core resin composition is preferably 0.8 or more, more preferably 0.9 or more, and even more preferably 1.
- a sheath part sheath part consists of a sheath part resin composition containing a polyamide.
- the type of polyamide is not particularly limited. For example, nylon 6, nylon 6,6, nylon 4,6, nylon 12, nylon 6,10, nylon 6,12, polyamide 6T, polyamide 9T, polyamide 10T, and those as a base It is preferably at least one resin selected from the group consisting of a modified polyamide 6T, a modified polyamide 9T, and a modified polyamide 10T in which a modifying monomer is copolymerized, particularly preferably nylon 6,6 and nylon 6.
- polyamide of the sheath used in the present invention a good tactile sensation similar to human hair is obtained by using a resin in which nylon 6, 6 and nylon 6 are mixed.
- the mass ratio of nylon 6,6 and nylon 6 in the sheath is preferably 70/30 to 95/5, and more preferably 80/20 to 90/10.
- the mass ratio of nylon 6,6 in the sheath is less than 70/30, the heat resistance tends to be low, and when it exceeds 95/5, the effect of improving the tactile sensation cannot be obtained.
- the sheath resin composition preferably contains only polyamide as a resin component, but may contain another resin.
- the polyamide / total resin component mass ratio in the sheath resin composition is preferably 0.8 or more, more preferably 0.9 or more, and even more preferably 1.
- At least one (preferably both) of the flame retardant core resin composition and the core resin composition may contain a flame retardant.
- a flame retardant By adding a flame retardant to at least one of the core resin composition and the core resin composition, the flame retardant is dispersed at the interface between the polyester in the core and the polyamide in the sheath, thereby improving the peel resistance. It is possible to impart flame retardancy.
- flame retardants include brominated flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants and hydrated metal compounds. The combination of brominated flame retardants and flame retardant aids is preferred because it has the highest flame retardant effect. .
- brominated flame retardants examples include brominated polystyrene flame retardants, ethylene bistetrabromophthalimide flame retardants, bis (pentabromophenyl) ethane flame retardants, brominated epoxy flame retardants, brominated phenoxy flame retardants, bromine Benzyl acrylate flame retardant, brominated phenol flame retardant, polydibromophenylene oxide flame retardant and the like.
- a brominated epoxy resin or a brominated phenoxy resin is preferable in consideration of the balance of flame retardancy, processability, and transparency of raw yarn.
- the addition amount of the brominated flame retardant is preferably 3 to 30 parts by mass, more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the polyester in the core or the polyamide in the sheath. If it is less than 3 parts by mass, flame retardancy cannot be obtained, and if it exceeds 30 parts by mass, poor dispersion with the resin occurs and spinnability deteriorates.
- a flame retardant aid in combination with the above brominated flame retardant.
- the flame retardant aid include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, zinc borate, and zinc stannate. Of these, antimony trioxide is preferable from the balance between drip resistance and transparency of the raw yarn.
- the addition amount of the flame retardant aid is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polyester in the core or the polyamide in the sheath.
- the amount is less than 0.1 parts by mass, the effect of the flame retardant aid is low.
- the amount exceeds 10 parts by mass, yarn breakage occurs due to poor dispersion, and stable spinning becomes difficult.
- the flame retardant aid is preferably in the range of an average particle size of 0.5 to 10 ⁇ m and more preferably in the range of an average particle size of 1 to 8 ⁇ m from the viewpoint of transparency and processability of the raw yarn. If it is less than 0.5 ⁇ m, poor dispersion due to aggregation occurs, and if it exceeds 10 ⁇ m, a problem of clouding occurs.
- At least one (preferably both) of the core resin composition and the core resin composition may contain a compatibilizing agent.
- a compatibilizer By adding a compatibilizer to at least one of the core resin composition and the core resin composition, the peel resistance is improved at the interface between the core and the sheath, and iron curling can be performed at a higher temperature. become.
- compatibilizer examples include maleic anhydride modified polymer, ethylene / butyl acrylate, maleic anhydride modified product, polyvalent carbodiimide, carbodiimide modified isocyanate, styrene-acrylonitrile-glycidyl methacrylate random copolymer, epoxy-styrene-acrylonitrile copolymer micro Gel, styrene-acrylonitrile-maleic anhydride copolymer, LLDPE-maleic anhydride graft polymer, polyolefin-maleic anhydride graft polymer, polyolefin-glycidyl methacrylate graft polymer, modified polyolefin, styrene / maleic acid half ester Examples thereof include a polymer, a styrene / maleic anhydride copolymer, and a styrene / maleic acid half ester copolymer.
- the terminal carboxyl group of the polyester in the core part and the terminal amino group of the polyamide in the sheath part react via a compatibilizing agent, the interfacial peeling between the core part and the sheath part is suppressed. preferable.
- the amount of the compatibilizing agent added is preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the polyester in the core or the polyamide in the sheath, and if it is less than 0.5 parts by mass, the effect of improving the peel resistance is improved. If it is small and exceeds 3 parts by mass, the decrease in the viscosity or increase in the viscosity of the polyester in the core or the polyamide in the sheath becomes remarkable, which is not preferable from the viewpoint of workability.
- polyester of the core used in the present invention a good tactile sensation similar to human hair can be obtained by using a resin in which polyethylene terephthalate and polybutylene terephthalate or polypropylene terephthalate are mixed.
- At least one (preferably both) of the core resin composition and the core resin composition of other components if necessary, additives such as heat-resistant agents, light stabilizers, fluorescent agents, antioxidants, antistatic Agents, pigments, dyes, plasticizers, lubricants, and the like can be included.
- additives such as heat-resistant agents, light stabilizers, fluorescent agents, antioxidants, antistatic Agents, pigments, dyes, plasticizers, lubricants, and the like can be included.
- a colorant such as a pigment or a dye
- a pre-colored fiber can be obtained.
- the method for producing an artificial hair fiber having a core-sheath structure according to the present invention is not particularly limited as long as it is a method for producing an artificial hair fiber having a core-sheath structure.
- two methods for forming a core part and for forming a sheath part are used. It can be obtained using a melt compound spinning extruder composed of an extruder.
- melt spinning process After the above-mentioned flame retardant, compatibilizer, particles and other additives are dry-blended in a predetermined ratio to a thermoplastic resin such as polyester in the core and polyamide in the sheath, a kneader Is melt-kneaded to obtain a core resin composition pellet and a sheath resin composition pellet.
- 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 core resin composition pellets and the sheath resin composition pellets obtained by melt kneading are each independently dried.
- a known apparatus such as a vacuum dryer or a hopper dryer can be appropriately selected and used.
- the moisture content of the pellet is preferably 100 ppm or less (100 mg / kg or less).
- the moisture content of the pellet is preferably 1000 ppm or less (1000 mg / kg or less).
- the dried core resin composition pellets are charged into an extruder for core configuration, and the dried sheath resin composition pellets are charged into an extruder for sheath configuration.
- Each core resin composition pellet and sheath resin composition pellet are melted and kneaded in an extruder so that the core resin composition becomes the core and the sheath resin composition becomes the sheath.
- melt spun from a core-sheath type composite nozzle 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, a die, etc., and it is cooled and solidified below the glass transition point by air cooling with a cold air cylinder.
- a spinning oil agent is applied using an oil supply applying device. Further, the temperature and length of the cold air tower, the temperature and spraying amount of the cold air tower, 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.
- the spun yarn may be cooled in a water tank containing cooling water to control the fineness. Thereafter, the fiber is scraped off by a winder, and a core-sheath type undrawn yarn can be obtained.
- the scraping speed is not particularly limited, but is preferably in the range of 50 to 300 m / min.
- the unstretched yarn obtained is subjected to a stretching process by a stretching machine in order to improve the tensile strength of the fiber.
- the stretching conditions are not particularly limited, and the target artificial hair having a core-sheath structure is set by setting the stretching ratio to 2.5 to 5.0 times, the stretching speed to 10 to 500 m / min, and the temperature to 25 to 150 ° C. Fiber can be obtained.
- the stretching method There are no particular limitations on the stretching method, but the unstretched yarn is wound around a bobbin and then stretched in a step different from the melt spinning step, or continuously from the melt spinning step without being wound around the bobbin. Any of direct spinning and drawing methods for drawing may be used.
- the 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 drawn yarn may be heat-treated at about 1 to 30%.
- the temperature condition of this heat treatment it is preferable to carry out in an atmosphere with an atmospheric temperature of 150 to 250 ° C.
- the atmosphere gas used for the heat treatment is not particularly limited, but an inert gas can be used in addition to the atmosphere. Nitrogen, argon, or the like may be used as the inert gas, but it is preferable to use air from the viewpoint of cost.
- the undrawn yarn is subjected to hot drawing and heat treatment, and the fineness is 10 to 100 dtex.
- the lower limit value of the fineness of the artificial hair fiber having the core-sheath structure is more preferably 20 dtex or more, and further preferably 35 dtex or more.
- the upper limit of the fineness of the core-sheath artificial hair fiber is more preferably 90 dtex or less, and still more preferably 80 dtex or less.
- the manufactured artificial hair fiber can be applied with a treatment agent containing an oil such as silicone to improve the tactile sensation and the like.
- the treatment agent may be applied before the artificial hair fiber is processed into a hair product, during the processing, or at any stage after the processing. More suitable in terms of sex.
- the hair ornament 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 artificial hair fibers 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 screw temperature of the two extruders is adjusted so that the nozzle temperature is 300 ° C., the discharge amount is 30 g / min after the steady state is reached, and the core-sheath composition ratio is 50/50.
- the rotation speed of the gear pump was determined.
- the strand was melt-spun in the vertical direction from the die, and the undrawn yarn was wound at a constant speed on a take-up machine installed at a position 2 m immediately below the nozzle. At this time, the temperature and air volume of the cold air tower and the take-up speed of the take-up machine were adjusted so that the fineness of the undrawn yarn was about 210d.
- Stretching process stretching was performed by a hot water stretching one-stage stretching method, and stretching was performed 3.5 times under the condition of a hot water bath temperature of 90 ° C. 4).
- Heat treatment process The drawn yarn having a core-sheath structure was heat-treated at 190 ° C. for 5 minutes using a hot-air annealing layer to obtain an artificial hair fiber having a fineness of 60 d.
- Examples 2 to 19, Comparative Examples 1 to 4> Examples 2 to 19 and Comparative Examples 1 to 4 were prepared in the same manner with the formulations shown in Tables 1 to 3.
- Processability and the obtained artificial hair fiber were evaluated for peelability, tactile sensation, and curling property according to the evaluation method and criteria described below.
- PET1 Polyethylene terephthalate (made in-house, melt viscosity 65 Pa ⁇ s)
- PET2 Polyethylene terephthalate (Mitsui Chemicals, J125S, melt viscosity 145 Pa ⁇ s)
- PET3 Polyethylene terephthalate (made in-house, melt viscosity 204 Pa ⁇ s)
- PET4 Polyethylene terephthalate (Mitsui Chemicals, J055, melt viscosity 450 Pa ⁇ s)
- PET5 Polybutylene terephthalate (manufactured by DuPont, S600F20, melt viscosity 118 Pa ⁇ s)
- PET6 Polytrimethylene terephthalate (manufactured by DuPont, Sorona EP3301NC010, melt viscosity 132 Pa ⁇ s)
- PA1 Polyamide 66 (made by Toray Industries, Amil
- the evaluation methods and criteria for each evaluation item are as follows.
- the peel resistance is obtained by using a fiber bundle sample in which artificial hair fibers are bundled to a length of 200 mm and a mass of 1.0 g, and heating the tip of the fiber bundle sample with a hair iron for 10 seconds. Evaluation was made by visually confirming the protrusion of the polyester at the core due to the difference in heat shrinkage of the polyamide. It judged by the temperature of the hair iron which this heat peeling produces, and evaluated as follows. (Double-circle): Thermal peeling does not arise on the conditions of the hair iron 220 degreeC. ⁇ : Thermal peeling did not occur under the condition of a hair iron at 200 ° C, but thermal peeling occurred at 220 ° C. X: Thermal peeling occurred under the condition of a hair iron at 200 ° C.
- ⁇ Tactile sense> For the tactile sensation, a fiber bundle sample in which artificial hair fibers were bundled to a length of 250 mm and a mass of 20 g was used. Artificial hair fiber treatment engineers (practice experience 5 years or more) were judged by the touch of 10 people and evaluated according to the following evaluation criteria. ⁇ : Nine or more engineers evaluated that tactile sensation was good ⁇ : Seven or eight engineers evaluated that tactile sensation was good ⁇ : Six or less engineers evaluated that tactile sensation was good What
- the core / sheath mass ratio is 40/60 to 90/10 and the viscosity ratio a / b is 0.5 to 2.5, so that it has a good tactile sensation similar to human hair, and It was found that an artificial hair fiber excellent in curl retention was obtained. It was also found that by using a brominated flame retardant together, the brominated flame retardant is dispersed at the interface between the polyester at the core and the polyamide at the sheath, thereby improving the peel resistance and imparting flame retardancy. Furthermore, it has been found that by adding a compatibilizing agent to the polyester at the core and the polyamide at the sheath, the peel resistance is improved and iron curling can be performed at a higher temperature. Further, it was found that the tactile sensation can be made closer to human hair by using a polyester in which the core is made of a resin in which polyethylene terephthalate and polybutylene terephthalate or polytrimethylene terephthalate are mixed.
- the artificial hair fiber having the core-sheath structure of the present invention By using the artificial hair fiber having the core-sheath structure of the present invention, it is possible to obtain a hair product (head ornament product) having a good tactile sensation similar to human hair and excellent in curl retention. Thereby, a wig (wig), a hair piece, a braid
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Abstract
Description
(1)芯部と前記芯部を覆う鞘部とからなる芯鞘構造を有する人工毛髪繊維であって、前記芯部がポリエステルを含む芯部樹脂組成物からなり、前記鞘部がポリアミドを含む鞘部樹脂組成物からなり、前記芯部及び前記鞘部の芯/鞘質量比が、40/60~90/10であり、前記芯部樹脂組成物のポリエステルの溶融粘度aと前記鞘部樹脂組成物のポリアミドの溶融粘度bの粘度比a/bが0.5~2.5であることを特徴とする人工毛髪繊維。
(2)前記芯部樹脂組成物は、臭素化ベンジルアクリレート、臭素化フェノール、ポリジブロモフェニレンオキシド、臭素化ポリスチレン、エチレンビステトラブロモフタルイミド、ビス(ペンタブロモフェニル)エタン、臭素化エポキシ、臭素化フェノキシ、臭素化ポリカーボネートおよび臭素含有トリアジン化合物よりなる群から選ばれる少なくとも一種の臭素系難燃剤を含有する(1)に記載の人工毛髪繊維。
(3)前記鞘部樹脂組成物は、臭素化ベンジルアクリレート、臭素化フェノール、ポリジブロモフェニレンオキシド、臭素化ポリスチレン、エチレンビステトラブロモフタルイミド、ビス(ペンタブロモフェニル)エタン、臭素化エポキシ、臭素化フェノキシ、臭素化ポリカーボネートおよび臭素含有トリアジン化合物よりなる群から選ばれる少なくとも一種の臭素系難燃剤を含有する(1)または(2)に記載の人工毛髪繊維。
(4)前記芯部樹脂組成物は、ポリエステル100質量部に対し、前記臭素系難燃剤の添加量が3~30質量部である(2)または(3)に記載の人工毛髪繊維。
(5)前記鞘部樹脂組成物は、ポリアミド100質量部に対し、前記臭素系難燃剤の添加量が3~30質量部である(3)または(4)に記載の人工毛髪繊維。
(6)前記芯部樹脂組成物は、ポリエステル100質量部に対し、相溶化剤0.5~3質量部を含有する(1)~(5)のいずれか一項に記載の人工毛髪繊維。
(7)前記鞘部樹脂組成物は、ポリアミド100質量部に対し、相溶化剤0.5~3質量部を含有することを特徴とする(1)~(6)のいずれか一項に記載の人工毛髪繊維。
(8)前記芯部樹脂組成物のポリエステルがポリエチレンテレフタレートおよびポリブチレンテレフタレートからなり、前記ポリエチレンテレフタレートおよびポリブチレンテレフタレートの質量比が、40/60~90/10であることを特徴とする(1)~(7)のいずれか一項に記載の人工毛髪繊維。
(9)前記芯部樹脂組成物のポリエステルがポリエチレンテレフタレートおよびポリプロピレンテレフタレートからなり、前記ポリエチレンテレフタレーおよびポリトリメチレンテレフタレートの質量比が、40/60~90/10であることを特徴とする(1)~(7)のいずれか一項に記載の人工毛髪繊維。
(10)前記鞘部樹脂組成物のポリアミドがナイロン6,6およびナイロン6からなり、前記ナイロン6,6およびナイロン6の質量比が、70/30~95/5であることを特徴とする(1)~(9)のいずれか一項に記載の人工毛髪繊維。
1.人工毛髪繊維
本発明の人工毛髪繊維は、芯部と前記芯部を覆う鞘部とからなる芯鞘構造を有する人工毛髪繊維であって、前記芯部がポリエステルを含む芯部樹脂組成物からなり、前記鞘部がポリアミドを含む鞘部樹脂組成物からなり、前記芯部及び前記鞘部の芯/鞘質量比が、40/60~90/10であり、前記芯部樹脂組成物のポリエステルの溶融粘度aと前記鞘部樹脂組成物のポリアミドの溶融粘度bの粘度比a/bが0.5~2.5であり、適宜、臭素系難燃剤及び相溶化剤を含有する。
芯部と鞘部の芯/鞘質量比は、40/60~90/10であり、50/50~85/15が好ましい。芯/鞘の質量比が40/60未満の場合は、鞘部のポリアミドが大気中の水分を吸収し、弾性率が低下することでカールを施した初期の状態から時間が経過するに従って、カール保持性が悪くなる。90/10を超過する場合は、鞘部のポリアミドの層が薄いため、人毛に似た良好触感が得られなくなる。
ポリエステル又はポリアミドの溶融粘度は、ポリエステルペレットまたはポリアミドペレットの吸水率を100ppm以下になる様に除湿乾燥し、サンプル量20cc、設定温度285℃、ピストンスピード200mm/min、キャピラリー長20mm、キャピラリー径1mmの条件で測定した値である。測定機器は東洋精機製作所社製のキャピログラフ1Dで溶融粘度を用いた。
芯部は、ポリエステルを含む芯部樹脂組成物からなる。ポリエステルの種類は特に限定されないが、ポリエチレンテレフタレート、ポリトリメチレンテレフタレートおよびポリブチレンテレフタレートから選ばれた少なくとも一種の樹脂であるのが好ましい。
鞘部がポリアミドを含む鞘部樹脂組成物からなる。ポリアミドの種類は特に限定されないが、例えば、ナイロン6、ナイロン6,6、ナイロン4,6、ナイロン12、ナイロン6,10、ナイロン6,12、ポリアミド6T、ポリアミド9T、ポリアミド10T及びそれらをベースに変性用モノマーを共重合させた変性ポリアミド6T、変性ポリアミド9T及び変性ポリアミド10Tからなる群から選ばれた少なくとも1種の樹脂であるのが好ましく、特に好ましくはナイロン6,6、ナイロン6である。
芯部樹脂組成物及び芯部樹脂組成物の少なくとも一方(好ましくは両方)は、難燃剤を含有してもよい。芯部樹脂組成物及び芯部樹脂組成物の少なくとも一方に難燃剤を添加することで、芯部のポリエステルと鞘部のポリアミドの界面に難燃剤が分散することで耐剥離性が向上し、同時に難燃性を付与することが可能である。難燃剤としては、臭素系難燃剤やリン系難燃剤、窒素系難燃剤や水和金属化合物などがあるが、臭素系難燃剤と難燃助剤の組み合わせが最も難燃性の効果が高く好ましい。
芯部樹脂組成物及び芯部樹脂組成物の少なくとも一方(好ましくは両方)は、相溶化剤を含有してもよい。芯部樹脂組成物及び芯部樹脂組成物の少なくとも一方に相溶化剤を添加することで、芯部と鞘部の界面で耐剥離性が向上し、より高い温度でアイロンカールをすることが可能になる。
芯部樹脂組成物及び芯部樹脂組成物の少なくとも一方(好ましくは両方)には、必要に応じて添加剤、例えば、耐熱剤、光安定剤、蛍光剤、酸化防止剤、静電防止剤、顔料、染料、可塑剤、潤滑剤等を含有させることができる。顔料、染料等の着色剤を含有させることにより、予め着色された繊維(いわゆる原着繊維)を得ることができる。
以下に、人工毛髪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。
芯部のポリエステル及び鞘部のポリアミドなどの熱可塑性樹脂に、上述した難燃剤、相溶化剤、粒子等の添加剤を所定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し、芯部樹脂組成物ペレット及び鞘部樹脂組成物ペレットを得る。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、例えば一軸押出機、二軸押出機、ロール、バンバリーミキサー、ニーダーなどがあげられる。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。
得られた未延伸糸は、繊維の引張強度を向上させるため、延伸機で延伸処理を実施する。延伸条件も特に限定されるものではなく、延伸倍率2.5~5.0倍、延伸速度10~500m/min、温度を25~150℃に設定して、目的とする芯鞘構造の人工毛髪繊維を得ることができる。延伸処理方法は特に限定されないが、未延伸糸を一旦ボビンに巻き取ってから溶融紡糸工程とは別の工程にて延伸する2工程法や、ボビンに巻き取ることなく溶融紡糸工程から連続して延伸する直接紡糸延伸法のいずれの方法によってもよい。また、延伸処理は、1度で目的の延伸倍率まで延伸する1段延伸法、又は2回以上の延伸によって目的の延伸倍率まで延伸する多段延伸法で行なわれる。熱延伸処理における加熱手段としては、加熱ローラ、ヒートプレート、スチームジェット装置、温水槽などを使用することができ、これらを適宜併用することもできる。
延伸処理を施した繊維は、延伸時に残留応力が発生するため、最終的な製品として人工毛髪の品質を確保する上で、熱処理により残留応力を除去するが好ましい。この熱処理と同時に場合によっては、1~30%程度、延伸糸を熱処理処理することも可能である。
人工毛髪繊維は、単独で頭髪製品(頭飾製品)に用いてもよいが、人毛や他の人工毛髪を混合して用いてもよい。頭髪製品は、ウィッグ(かつら)、ヘアピース、ブレード、エクステンンョンヘアー、人形の頭髪等であり、人工毛髪繊維の用途は特に限定されない。また、頭髪製品以外にも付け髭、付け睫毛、付け眉毛等に用いることもできる。
<実施例1>
表1に示す芯部樹脂組成物のペレットを含有水分率が100ppm以下(100mg/kg以下)になるように、ホッパードライヤー(株式会社カワタ製、チャレンジャーIII)を使用し、温度が一定になった状態から120℃で12時間、除湿乾燥を行った。また、表1に示す芯部樹脂組成物のペレットについても含有水分率が1000ppm以下(1000mg/kg以下)になるように、80℃で12時間、同様な操作を実施した。
押出機には、Φ20mm溶融紡糸押出機(株式会社ジー・エム・エンジニアリング、フルフライトスクリュー(圧縮比2.3))を2台組み合わせて使用した。ダイスには、芯鞘型複合のノズル(孔数36、穴径1mm)を用いた。芯部および鞘部を構成する押出機の設定条件として、芯部を構成する押出機のシリンダー温度を295℃に設定し、鞘部を構成する押出機のシリンダーの温度を315℃に設定した。また、ノズル温度300℃になるように調整し、定常状態になってから吐出量30g/min、芯鞘構成比が50/50の比になるように、2台の押出機のスクリュー回転数、ギヤポンプの回転数を決定した。ストランドは、ダイスから鉛直方向に溶融紡出させ、ノズル直下2mの位置に設置した引取機に未延伸糸を一定速度で巻き取った。この際、未延伸糸の繊度が約210dになるように冷風塔の温度と風量および引取機の引取速度とを調節した。
延伸は、熱水延伸1段延伸法で行ない、温水バスの温度90℃の条件下で3.5倍に延伸した。
4.熱処理工程
芯鞘構造の延伸糸を、熱風アニール層を使用し、190℃で5分間熱処理を行い、繊度60dの人工毛髪繊維を得た。
<実施例2~19、比較例1~4>
実施例2~19、比較例1~4も同様にして、表1~3の処方で作成した。
<ポリエステル>
PET1:ポリエチレンテレフタレート(自社製、溶融粘度65Pa・s)
PET2:ポリエチレンテレフタレート(三井化学社製、J125S、溶融粘度145Pa・s)
PET3:ポリエチレンテレフタレート(自社製、溶融粘度204Pa・s)
PET4:ポリエチレンテレフタレート(三井化学社製、J055、溶融粘度450Pa・s)
PET5:ポリブチレンテレフタレート(デュポン社製、S600F20、溶融粘度118Pa・s)
PET6:ポリトリメチレンテレフタレート(デュポン社製、ソロナEP3301NC010、溶融粘度132Pa・s)
<ポリアミド>
PA1:ポリアミド66(東レ株式会社製、アミランCM3001-N、溶融粘度、66Pa・s)
PA2:ポリアミド66(デュポン社製、Zytel 101、140Pa・s)
PA3:ポリアミド66(デュポン社製、Zytel 42A、249Pa・s)
PA4:ポリアミド6 (自社試作製造、56Pa・s)
<難燃剤>
難燃剤1:臭素化ベンジルアクリレート系難燃剤(ICL JAPAN製、FR-1025)
難燃剤2:臭素化エポキシ系難燃剤(阪本薬品工業製、SR-T20000)
<相溶化剤>
無水マレイン酸変性ポリマー(デュポン製、フサボンド、A560)
耐剥離性は、人工毛髪繊維を長さ200mm、質量1.0gに束ねた繊維束サンプルを使用し、ヘアアイロンで繊維束サンプルの先端を10秒間加熱した時に、芯部のポリエステルと鞘部のポリアミドの熱収縮の差による芯部のポリエステルの突出を目視により確認することで、評価した。この熱剥離が生じるヘアアイロンの温度により判定し、次のとおり評価した。
◎:ヘアアイロン220℃の条件で熱剥離が生じない。
○:ヘアアイロン200℃の条件で熱剥離が生じないが、220℃で熱剥離が生じた。
×:ヘアアイロン200℃の条件で熱剥離が生じた。
触感は、人工毛髪繊維を長さ250mm、質量20gに束ねた繊維束サンプルを使用した。人工毛髪繊維処理技術者(実務経験5年以上)10人の手触りによる判定で、次の評価基準で評価した。
◎:技術者9人以上が、触感が良いと評価したもの
○:技術者の7人又は8人が、触感が良いと評価したもの
×:技術者の6人以下が、触感が良いと評価したもの
カール性は、人工毛髪繊維を長さ500mm、質量2.0gに束ねた繊維束サンプルを使用した。20mmφのアルミ製筒に巻き付け乍ら両端を固定し、100℃のスチーム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おり、次の評価基準で評価した。
◎:値が0.75未満
○:値が0.75以上0.85未満
×:値が0.85以上
比較例1では、芯/鞘質量比が小さすぎるため、カール保持性が悪かった。
比較例2では、芯/鞘質量比が大きすぎるため、触感が悪かった。
<比較例3、4>
比較例3では、粘度比a/bが大きすぎるため、耐剥離性が悪かった。また、比較例4では、粘度比a/bが小さすぎるため、耐剥離性が悪かった。
Claims (10)
- 芯部と前記芯部を覆う鞘部とからなる芯鞘構造を有する人工毛髪繊維であって、前記芯部がポリエステルを含む芯部樹脂組成物からなり、前記鞘部がポリアミドを含む鞘部樹脂組成物からなり、前記芯部及び前記鞘部の芯/鞘質量比が、40/60~90/10であり、前記芯部樹脂組成物のポリエステルの溶融粘度aと前記鞘部樹脂組成物のポリアミドの溶融粘度bの粘度比a/bが0.5~2.5であることを特徴とする人工毛髪繊維。
- 前記芯部樹脂組成物は、臭素化ベンジルアクリレート、臭素化フェノール、ポリジブロモフェニレンオキシド、臭素化ポリスチレン、エチレンビステトラブロモフタルイミド、ビス(ペンタブロモフェニル)エタン、臭素化エポキシ、臭素化フェノキシ、臭素化ポリカーボネートおよび臭素含有トリアジン化合物よりなる群から選ばれる少なくとも一種の臭素系難燃剤を含有する請求項1に記載の人工毛髪繊維。
- 前記鞘部樹脂組成物は、臭素化ベンジルアクリレート、臭素化フェノール、ポリジブロモフェニレンオキシド、臭素化ポリスチレン、エチレンビステトラブロモフタルイミド、ビス(ペンタブロモフェニル)エタン、臭素化エポキシ、臭素化フェノキシ、臭素化ポリカーボネートおよび臭素含有トリアジン化合物よりなる群から選ばれる少なくとも一種の臭素系難燃剤を含有する請求項1または2に記載の人工毛髪繊維。
- 前記芯部樹脂組成物は、ポリエステル100質量部に対し、前記臭素系難燃剤の添加量が3~30質量部である請求項2または3に記載の人工毛髪繊維。
- 前記鞘部樹脂組成物は、ポリアミド100質量部に対し、前記臭素系難燃剤の添加量が3~30質量部である請求項3または4に記載の人工毛髪繊維。
- 前記芯部樹脂組成物は、ポリエステル100質量部に対し、相溶化剤0.5~3質量部を含有する請求項1~5のいずれか一項に記載の人工毛髪繊維。
- 前記鞘部樹脂組成物は、ポリアミド100質量部に対し、相溶化剤0.5~3質量部を含有することを特徴とする請求項1~6のいずれか一項に記載の人工毛髪繊維。
- 前記芯部樹脂組成物のポリエステルがポリエチレンテレフタレートおよびポリブチレンテレフタレートからなり、前記ポリエチレンテレフタレートおよびポリブチレンテレフタレートの質量比が、40/60~90/10であることを特徴とする請求項1~7のいずれか一項に記載の人工毛髪繊維。
- 前記芯部樹脂組成物のポリエステルがポリエチレンテレフタレートおよびポリプロピレンテレフタレートからなり、前記ポリエチレンテレフタレーおよびポリトリメチレンテレフタレートの質量比が、40/60~90/10であることを特徴とする請求項1~7のいずれか一項に記載の人工毛髪繊維。
- 前記鞘部樹脂組成物のポリアミドがナイロン6,6およびナイロン6からなり、前記ナイロン6,6およびナイロン6の質量比が、70/30~95/5であることを特徴とする請求項1~9のいずれか一項に記載の人工毛髪繊維。
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Cited By (8)
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WO2019172147A1 (ja) * | 2018-03-06 | 2019-09-12 | デンカ株式会社 | 人工毛髪用繊維束 |
WO2020066650A1 (ja) * | 2018-09-25 | 2020-04-02 | パイロットインキ株式会社 | 可逆熱変色性複合繊維 |
WO2020166262A1 (ja) * | 2019-02-15 | 2020-08-20 | 株式会社カネカ | 人工毛髪用芯鞘複合繊維、それを含む頭飾製品及びその製造方法 |
WO2021090735A1 (ja) * | 2019-11-07 | 2021-05-14 | デンカ株式会社 | 人工毛髪用繊維及びその製造方法、並びに、頭髪装飾品 |
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JP7408769B2 (ja) | 2020-03-03 | 2024-01-05 | 株式会社カネカ | 人工毛髪用芯鞘複合繊維、それを含む頭飾製品及びその製造方法 |
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KR20190004304A (ko) | 2019-01-11 |
CN112899799B (zh) | 2023-03-21 |
JP2022000552A (ja) | 2022-01-04 |
CN112899799A (zh) | 2021-06-04 |
CN109068780B (zh) | 2021-02-26 |
US20190090565A1 (en) | 2019-03-28 |
US10856598B2 (en) | 2020-12-08 |
CN109068780A (zh) | 2018-12-21 |
JPWO2017187843A1 (ja) | 2019-03-07 |
KR102286437B1 (ko) | 2021-08-04 |
JP7011581B2 (ja) | 2022-01-26 |
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