WO2012046748A1 - Fiber for artificial hair, and hair accessory formed from same - Google Patents

Abstract

The present invention pertains to a polyvinyl chloride resin fiber having a contraction stress of 70 µN/dtex or less at 130°C. It is possible to obtain an artificial hair product and fiber for artificial hair having a texture similar to human hair and exerting excellent styling properties by processing a fiber bundle for artificial hair containing 20 to 100 weight % of the aforementioned polyvinyl chlorine resin fiber and 0 to 80 weight % of a thermoplastic resin fiber which has a Young's modulus of 4 to 9 GPa and a contraction rate of 10% or less at 130°C and which comprises a composition excluding the polyvinyl chlorine resin.

Description

Artificial hair fibers and hair ornaments comprising the same

The present invention provides an artificial hair fiber having excellent styling properties and a soft and smooth touch close to human hair, an artificial hair fiber bundle, and a hair ornament, an artificial hair product comprising the same, and the artificial hair fiber and The present invention relates to a polyvinyl chloride resin fiber constituting a fiber bundle for artificial hair.

There are many materials such as polyvinyl chloride resin fibers, polyester resin fibers, and modacrylic resin fibers that are generally commercially available synthetic fibers for artificial hair. Each of these synthetic fibers has excellent properties derived from the raw materials, and has been used for headdress products in the field of specialty in accordance with the properties of each fiber. Furthermore, in recent years, products having a value relatively close to that of human hair products have been put on the market by mixing each fiber and using them in one head ornament product, and making use of each excellent characteristic in harmony. For example, polyvinyl chloride resin fibers have a soft touch close to human hair, are easily processed into an arbitrary style, and have little hair entanglement. Polyester resin fibers are strong and have excellent resilience when they are moved with a product on them, and they are highly durable because of their high form stability. Modacrylic resin fibers are lightweight and have a high volume feeling, and have a feature that a natural appearance can be obtained by utilizing surface irregularities. However, on the other hand, when mixing fibers of different materials, it is difficult to make full use of the properties of each fiber, and synthetic hair headdress products still have a commercial value comparable to human hair products. There is no actual situation.

The biggest challenge when using mixed fibers of different materials is that the optimum processing temperature differs depending on the material. In order to increase the commercial value of headdress products, it is necessary to improve the appearance, tactile sensation, and styling quality without sacrificing all of them, but in addition to selecting the composition ratio of each fiber and the fiber treatment agent Thus, it is important to heat at an appropriate temperature when imparting the curl shape. Specifically, by imparting a curl shape at an appropriate temperature, the elasticity and shape retention force are improved, thereby improving the pulsation and durability of use as a hair product. Furthermore, in a specific fiber treatment agent, by applying high-temperature heat, the fiber treatment agent becomes familiar with the fiber surface, and a smooth and moisturizing feeling (moisture feel) similar to human hair can be expressed. However, on the other hand, when heated at an excessively high temperature from the optimum temperature of the material, fusion occurs between the fibers, the flexibility is lost, and the fibers are bent due to thermal contraction, resulting in a gritty feel. In addition, when heated at an excessively low temperature, the shape cannot be retained sufficiently, and the styling property will be lowered. In general, curling is performed in accordance with an appropriate processing temperature of a material having the lowest heat resistance.

In particular, since the polyvinyl chloride resin has low heat resistance, and the deterioration of the quality due to the increase in temperature is remarkable, the temperature for imparting the curled shape is limited to 80 to 90 ° C. For this reason, especially when high heat-resistant fibers such as polyester resin fibers are mixed, the processing temperature is lower than the appropriate temperature of the polyester resin fibers, so it is not possible to make use of the inherent curl strength. In addition, the effect of improving the tactile sensation inherent to the fiber treatment agent cannot be fully exhibited. However, polyvinyl chloride resin fiber has very excellent properties as a fiber for hair, such as soft and smooth touch similar to human hair, curled style, and cost performance. It has been difficult, and the conventional technology has not been able to obtain a satisfactory level of overall quality.

Specifically, for example, Patent Documents 1 and 2 include examples in which a polyester resin fiber and a halogen-containing resin fiber, or a modacrylic resin fiber and a polyvinyl chloride resin fiber are mixed to impart curl at 100 ° C. or higher. Is described. These technologies have succeeded in developing merchandise superior to conventional products by mixing different materials and taking advantage of their characteristics. However, since the performance of the polyvinyl chloride resin fiber was not sufficient, there was still room for improvement from the viewpoint of tactile sensation, and it was not possible to provide merchandise comparable to human hair products.

Furthermore, several attempts have been made regarding polyvinyl chloride resin fibers for the purpose of solving the above-mentioned problems, but sufficient effects have not yet been obtained.

For example, Patent Document 3 describes a method for calculating curling conditions. However, simply reducing the shrinkage rate does not provide a sufficient effect of suppressing the generation of fiber bending, and the fibers become hard at high temperatures. Since the concept of tactile sensation was not taken into account, satisfactory quality could not be obtained as a hair product.

Patent Document 4 describes an example of blending a chlorinated polyvinyl chloride resin having a high chlorine content as an attempt to improve the heat resistance of the polyvinyl chloride resin fiber, but only by reducing the shrinkage rate. A satisfactory tactile sensation as a hair product could not be obtained.

None of the patent literatures have been studied for sufficiently obtaining the effect of the fiber treatment agent, and have not reached a level that satisfies the smooth and moisturizing feel required for hair products.

JP 2002-227019 A WO2005 / 082184 JP 2003-293213 A Japanese Patent No. 4491414

An object of the present invention is to provide a fiber for artificial hair and an artificial hair product that have excellent styling properties and have a soft and smooth feel close to human hair.

As a result of intensive studies to solve the above problems, the present inventors have made improvements in reducing the shrinkage stress to the polyvinyl chloride resin fiber and, if necessary, a fiber excellent in heat resistance and rigidity. It was found that a head decoration product that solves the above problems can be produced by selecting and processing the curl shape imparting temperature and shrinkage rate, and the fiber treatment agent, thereby completing the present invention. The principle of the present invention will be described below.

As described above, since the polyvinyl chloride resin fiber has a low softening temperature of the main component polyvinyl chloride resin, if it is processed at a temperature higher than 90 ° C., which exceeds the glass transition temperature, the fiber bends due to shrinkage. , It becomes a feeling of bad touch. This fiber bending occurs on the following principle. First, in the step of imparting a curl shape, a fiber bundle is wound spirally or concentrically on a cylindrical pipe and heated for a predetermined time in a state in which the shape is maintained, and then the brazed shape is stored in the fiber bundle, and then The process is completed by cooling and removing the fiber bundle from the pipe. At this time, if fibers with a large shrinkage difference are mixed, the fibers with a small shrinkage are pulled by the fibers with a small shrinkage by pulling the fibers with a small shrinkage, and when the temperature is high, the deflection is a fiber bending. It became the cause of the tactile deterioration. And in human tactile sensation, it has been found that when the angle of bending is less than 170 °, a feeling of roughness is felt. In addition, polyvinyl chloride resin fibers tend to bend at angles of less than 170 ° relative to other fibers such as modacrylic resin fibers and polyester resin fibers, and in addition, they are flexible by fusion between fibers. It has been found that the degree of deterioration of the tactile sensation is extremely large.

As a result of repeated investigations by the inventors, when the shrinkage stress of the fiber having a high shrinkage rate is small, the fiber having a low shrinkage rate plays a role of a support column and is less likely to bend. It has been found that when the rigidity is high, the shrinkage of the fiber having a large shrinkage rate is suppressed, and the fiber bending becomes difficult to occur. And by applying that principle, the shrinkage stress of polyvinyl chloride resin fibers that tend to bend fibers is reduced, and if necessary, the rigidity is higher than that of polyvinyl chloride resin fibers and the shrinkage is small. By mixing these, the curl shape was successfully imparted without increasing fiber bending even at a temperature higher than the conventional 90 ° C.

Further, the effect of increasing the temperature for imparting the curl shape also affects the tactile feel of the fiber treatment agent, and the familiarity between the fiber treatment agent and the fiber surface is improved by heating at a high temperature, particularly when an amino-modified silicone compound is used. It has been discovered that the fiber smoothness and the moisturizing feeling can be amplified compared to the case where the curl shape is imparted at a temperature of ℃ or lower. Furthermore, since the amino-modified silicone compound has the effect of suppressing the inter-fiber fusion of the polyvinyl chloride resin fibers, it is possible to ensure the flexibility of the fibers that has been lowered at the time of high temperature heating. It has been found that an excellent tactile sensation close to human hair can be obtained.

That is, the present invention has the following gist.

One of the characteristics of the present invention is a polyvinyl chloride resin fiber having a shrinkage stress at 130 ° C. of 70 μN / dtex or less.

Another feature of the present invention is a polyvinyl chloride resin fiber for artificial hair having a shrinkage stress at 130 ° C. of 70 μN / dtex or less.

Another feature of the present invention is that a thermoplastic resin fiber comprising 20 to 100% by weight of a polyvinyl chloride resin fiber having a shrinkage stress at 130 ° C. of 70 μN / dtex or less and a composition excluding the polyvinyl chloride resin. A fiber bundle for artificial hair containing 0 to 80% by weight.

Another feature of the present invention is that 20 to 100% by weight of polyvinyl chloride resin fiber having a shrinkage stress at 130 ° C. of 70 μN / dtex or less, Young's modulus of 4 to 9 GPa, and shrinkage at 130 ° C. Is a fiber bundle for artificial hair containing 10 to 80% by weight of thermoplastic resin fibers having a composition excluding polyvinyl chloride resin.

Another feature of the present invention is that the shrinkage rate of the polyvinyl chloride resin fiber at 130 ° C. is not lower than the shrinkage rate of the thermoplastic resin fiber at 130 ° C., and the shrinkage rate of the polyvinyl chloride resin fiber at 130 ° C. The fiber bundle for artificial hair, characterized in that the difference between the shrinkage rate and the shrinkage rate of thermoplastic resin fibers at 130 ° C. is 6% or less.

Another feature of the present invention is a fiber bundle for artificial hair in which the polyvinyl chloride resin fiber and the thermoplastic resin fiber contain an amino-modified silicone compound.

Another feature of the present invention is a fiber bundle for artificial hair in which the polyvinyl chloride resin fiber contains 0.07 to 0.5 omf% of a polyalkylene oxide compound having a weight average molecular weight of 2000 to 25000.

Another feature of the present invention is a fiber bundle for artificial hair in which the polyvinyl chloride resin fiber contains 0 to 0.5 omf% of a silicone compound.

Another feature of the present invention is that a thermoplastic resin fiber comprising 20 to 100% by weight of a polyvinyl chloride resin fiber having a shrinkage stress at 130 ° C. of 70 μN / dtex or less and a composition excluding the polyvinyl chloride resin. An artificial hair product obtained by processing a fiber bundle for artificial hair containing 0 to 80% by weight.

The present invention provides an artificial hair fiber and an artificial hair product that are excellent in styling properties and have a soft and smooth feel close to human hair.

FIG. 4 is a diagram showing the measurement results of shrinkage stress relating to the polyvinyl chloride resin fibers described in Production Example 1-4 of the present invention, PVC-1 being a conventional product and PVC-2 to PVC-4 being improved products of the present invention.

Details of the present invention will be described below.

The fiber bundle for artificial hair of the present invention has 20 to 100% by weight of polyvinyl chloride resin fiber having a shrinkage stress at 130 ° C. of 70 μN / dtex or less, Young's modulus of 4 to 9 GPa, and shrinkage at 130 ° C. of 10%. It is characterized by comprising 0 to 80% by weight of thermoplastic resin fibers having the following composition excluding polyvinyl chloride resin.

The fiber bundle in the present invention refers to an aggregate of two or more single fibers of 20 to 100 dtex, and may be fixed so that the aggregate of single fibers does not collapse or may not be fixed. . Synthetic fibers for artificial hair are usually manufactured as continuous fiber bundles of several hundreds of meters, cut into an arbitrary length at the time of product processing, and then commercialized by mixing fibers or imparting a curled shape. The fiber bundle in the present invention is not particularly limited, and unless otherwise specified, for example, refers to a continuous fiber bundle during production, a fiber bundle cut during product processing, a fiber bundle in a hair product, and the like. .

The polyvinyl chloride resin fiber used in the present invention is a fiber mainly composed of a polyvinyl chloride resin and has a small shrinkage stress. In general, the shrinkage stress tends to increase when the shrinkage rate is large. However, even if there is a potential shrinkage strain, it is possible to reduce the stress generated at the time of shrinkage, thereby suppressing the occurrence of fiber bending. . In order to reduce the shrinkage stress, a method of performing relaxation heat treatment for a long time at a high temperature of, for example, 110 ° C. or more at the time of fiber production is effective, and the shrinkage stress can be lowered even with the same shrinkage rate. However, the method of reducing the shrinkage stress is not limited to this and can be used. In the polyvinyl chloride resin fiber, the shrinkage stress generally has a peak in the vicinity of 130 ° C. as shown in FIG. 1, and a preferable value of the shrinkage stress in the present invention is specifically a shrinkage stress at 130 ° C. of 70 μN. / Dtex or less is preferable, preferably 50 μN / dtex or less, and more preferably 40 μN / dtex or less. When the shrinkage stress exceeds 70 μN / dtex, the effect of the thermoplastic resin fiber that supports the polyvinyl chloride resin fiber and suppresses the shrinkage is not sufficient, so that the polyvinyl chloride resin fiber bends, and the fiber bending does not occur. Occurs and feels worse.

The polyvinyl chloride resin fiber used in the present invention can be suitably used as a polyvinyl chloride resin fiber for artificial hair.

The composition ratio of the polyvinyl chloride resin fiber used in the present invention in the fiber bundle for artificial hair is 20 to 100% by weight, preferably 30 to 75% by weight, and more preferably 40 to 60% by weight. If the composition ratio in the fiber bundle for artificial hair is lower than 20% by weight, the soft tactile and style properties of the polyvinyl chloride resin fiber are insufficient, and satisfactory merchandise cannot be obtained, and the merchantability tends to decrease. is there.

Further, as the polyvinyl chloride resin fiber used in the present invention, 0.07 to 0.5 omf% of a polyalkylene oxide compound having a weight average molecular weight of 2000 to 25000 in a fiber bundle state before being processed into a product, and a silicone type A compound in which a compound is supported on the surface of 0 to 0.5 omf% fiber can be preferably used.

“Supported on the surface of the fiber” means a state in which a specific compound adheres to the surface layer of the fiber, and excludes components that have penetrated into the fiber and can no longer be removed. In the present invention, ethanol / cyclohexane = 50 wt% / 50 wt% is used as a solvent that does not penetrate into the inside of the polyvinyl chloride resin fiber, and the weight of the compound extracted when the fiber is immersed in this solvent is handled as the supported amount. .

As a method of reducing the shrinkage stress of the fibers described above, when the temperature of the relaxation heat treatment is increased, the conventional polyvinyl chloride resin fibers for hair cause fusion between the fibers, and the softness close to human hair that the material has There was a problem that it was impossible to get a good touch. This usually occurs because the performance of the process oil used for the purpose of suppressing fusion is not sufficient. In polyvinyl chloride resin fibers, mixed emulsions composed of nonionic surfactants, cationic surfactants, oil components such as ester oils, etc. have been used as process oils. Were low molecular weight components having a weight average molecular weight of less than 1500. When high molecular weight components are used, the feel becomes sticky and it is difficult to wash thoroughly even when changing another oil during product processing, so that a satisfactory feel can be obtained even in the final product. It was because there was a problem. However, as a result of repeated studies by the inventors, a fiber treatment agent component having a weight average molecular weight of less than 1500 is gradually penetrated into the fiber when heated at 100 ° C. or higher while being supported on the surface of a vinyl chloride resin fiber. As a result, the residual amount of the fiber surface layer is greatly reduced, so that the effect of suppressing fusion is reduced, and further, the oil component that has penetrated into the inside of the fiber exhibits a plasticizing effect. I found that it caused an increase. As a result of repeated studies, when a polyalkylene oxide compound having a weight average molecular weight of 2000 to 25000 is used as a process oil, the oil does not penetrate into the fiber and can be maintained at a high temperature of 120 ° C. or higher. It has been found that a sufficient fusion suppression effect can be expressed. Furthermore, the oil agent improved the stickiness of the tactile sensation by adjusting the adhesion amount, and the combing property and the static electricity suppressing effect were good even with a small adhesion amount.

As the polyalkylene oxide compound used in the present invention, a polyalkylene oxide compound obtained by addition-polymerizing an alkylene oxide containing ethylene oxide to an organic compound having two active hydrogen groups can be suitably used. Examples of the organic compound having two active hydrogen groups include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1,6-hexanediol, and aniline. Among these, at least one compound can be suitably used. Examples of the alkylene oxide containing ethylene oxide include ethylene oxide and alkylene oxides having 3 to 30 carbon atoms. For example, propylene oxide, butylene oxide, styrene oxide, α-olefin epoxide, or glycidyl ethers can be used. Among these, at least one compound can be suitably used. Among these, from the viewpoint of tactile sensation, it is preferable that the number of carbon atoms is small, but a copolymer of ethylene oxide and propylene oxide is preferable because it needs fluidity at room temperature in order to obtain an effect of suppressing fusion. The addition polymerization of alkylene oxide can be carried out according to a known method, and may be random type or block type. The molecular weight is preferably 2000 to 25000 in terms of weight average molecular weight, preferably 5000 to 20000, and more preferably 10,000 to 18000. If the weight average molecular weight is less than 2000, the fiber feels harder because it penetrates into the fiber during heating and the effect of suppressing fusion is reduced, and if it is greater than 25000, even if the amount of adhesion is adjusted, the feeling of stickiness is felt. Become. In order to achieve both the tactile sensation and the antistatic effect, polyalkylene oxide compounds having different weight average molecular weights within the above range may be mixed.

The supported amount of the polyalkylene oxide compound used in the present invention on the fiber is preferably 0.07 to 0.5 omf%, preferably 0.07 to 0.3 omf%, more preferably 0.1 to 0.2 omf%. . When the supported amount with respect to the fiber is less than 0.07, the effect of suppressing fusion is insufficient, the fiber becomes hard, and the combing property and the effect of suppressing static electricity are insufficient. On the other hand, when the loading amount on the fiber is more than 0.5 omf%, the feeling of stickiness is felt, and the fiber is excessively converged to reduce the volume feeling.

The polyvinyl chloride resin fiber used in the present invention may carry a silicone compound in addition to the polyalkylene oxide compound. A silicone compound having a specific viscosity does not penetrate into the inside of the fiber as in the case of the polyalkylene oxide compound, and can provide a high fusion suppressing effect. Furthermore, when the silicone compound is an amino-modified silicone compound, good tactile sensation is obtained by performing heat treatment at a high temperature as described above, and fiber bending does not occur because heating is performed in a tension state particularly in the relaxation heat treatment step. Therefore, heating can be performed at a higher temperature than when the curled shape is imparted, and a higher tactile improvement effect can be obtained. However, since a silicone compound has a large charging effect, it cannot be used alone as an oil agent, and must be used in combination with a polyalkylene oxide compound.

As a silicone compound used in the present invention, a linear polydimethylsiloxane that is liquid at 23 ° C., or an amino group, an epoxy group, a carboxyl group, a polyether group, or a thiol group is introduced into the side chain of the polydimethylsiloxane to form a molecule. A compound generally referred to as a silicone oil having a methyl group or a hydroxyl group at the end can be preferably used. Further, a plurality of silicone compounds may be mixed on the fiber surface, and silsesquioxane having the above functional group may be mixed within a range that can maintain the stability of the emulsion. Among these, polydimethylsiloxane, amino group-modified dimethylsiloxane, and epoxy-modified dimethylsiloxane are preferable, and amino-modified dimethylsiloxane and dimethylsiloxane are more preferable. Amino-modified dimethylsiloxane has a better feel to the fiber surface at a relatively low temperature than other silicone compounds, and can provide a good tactile feel. By adding dimethylsiloxane in any proportion, a smoother tactile feel can be obtained. Obtainable. Among silicone compounds, silicone oil generally has a molecular weight generally defined by kinematic viscosity. In the present invention, a preferable kinematic viscosity is 500 to 20000 mm ² / s at 25 ° C., more preferably 1000 to 10,000 mm ² / s. s. If the kinematic viscosity is lower than 500 mm ² / s, the amount of penetration into the fiber increases, so that the effect of suppressing fusion is insufficient and the fiber becomes hard, and if it is higher than 20000 mm ² / s, it adheres uniformly to the fiber surface. This makes it difficult to obtain a sufficient effect of suppressing fusion and improving the tactile sensation.

The supported amount of the silicone compound used in the present invention on the fiber is preferably 0 to 0.5 omf%, preferably 0.02 to 0.3 omf%, more preferably 0.05 to 0.2 omf%. When the amount supported on the fiber is more than 0.5 omf%, the charging effect is great, and static electricity is generated, causing problems such as entanglement of single fibers during fiber processing.

In addition to the polyalkylene oxide compound and the silicone compound, the polyvinyl chloride resin fiber used in the present invention may contain an antistatic agent or a smoothing agent, but it is a mineral that penetrates into the fiber and exhibits a plasticizing effect. The adhesion amount of oil components such as oil and ester oil should be small, and the preferable adhesion amount of the oil component is 0.15 omf% or less, more preferably 0.07 omf% or less.

The polyvinyl chloride resin fiber used in the present invention is not particularly limited in the blending and production method, and can be produced using a conventionally known production method. However, the fineness suitable for hair fibers and the cross-sectional shape of the fiber can be used. In order to obtain the above, it is preferable to use a manufacturing method in the same field. One example will be described below.

The polyvinyl chloride resin fiber used in the present invention is a fiber mainly composed of a polyvinyl chloride resin, and the polyvinyl chloride resin fiber is used depending on the purpose as long as the quality and spinning stability of the fiber are not impaired. The well-known compounding agent used for a composition can be added. Specifically, for example, heat resistance improvers such as chlorinated vinyl chloride resins and AS resins, metal soap heat stabilizers, stabilizing aids such as β diketones, phosphites, polyols, plasticizers, UV absorbers, oxidation Inhibitors, antistatic agents, fillers, flame retardants, pigments and the like can be used. In some cases, special compounding agents such as a foaming agent, a crosslinking agent, a tackifier, a conductivity imparting agent, and a fragrance can be used.

The polyvinyl chloride resin used for the polyvinyl chloride resin fiber used in the present invention is particularly limited to a homopolymer resin that is a homopolymer of a conventionally known vinyl chloride or various conventionally known copolymer resins. is not. Examples of copolymer resins include vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl propionate copolymer resins and other vinyl chloride and vinyl ester copolymer resins, vinyl chloride-butyl acrylate copolymer resins, vinyl chloride-2-ethylhexyl acrylate. Representative examples include copolymer resins of vinyl chloride and acrylates such as copolymer resins, vinyl chloride-ethylene copolymer resins, vinyl chloride and olefins such as vinyl chloride-propylene copolymer resins, and vinyl chloride-acrylonitrile copolymer resins. Illustratively. A preferred vinyl chloride resin is a homopolymer resin which is a homopolymer of vinyl chloride. In the copolymer resin, the content of the comonomer is not particularly limited, and can be determined according to the moldability of the fiber, the properties of the fiber, and the like. However, when the softening temperature of the copolymer resin is low, the heat resistance may be lowered. Therefore, it is preferable to use a mixture with a homopolymer resin that is a homopolymer of vinyl chloride.

The viscosity average polymerization degree of the vinyl chloride resin used for the polyvinyl chloride resin fiber used in the present invention is preferably 450 or more in order to obtain sufficient strength and heat resistance as the fiber. In order to produce a safe fiber under an appropriate nozzle pressure, the degree of polymerization is preferably 1800 or less. In order to achieve these molding processability and fiber characteristics, when a vinyl chloride homopolymer resin is used, a region having a viscosity average polymerization degree of 650 to 1450 is particularly preferable. When a copolymer is used, the viscosity average degree of polymerization is particularly preferably in the range of 1000 to 1700, depending on the comonomer content. The viscosity average degree of polymerization was calculated according to JIS-K6721 by dissolving 200 mg of resin in 50 ml of nitrobenzene, measuring the specific viscosity of this polymer solution in a constant temperature bath at 30 ° C. using an Ubbelohde viscometer. .

The vinyl chloride resin used for the polyvinyl chloride resin fiber used in the present invention can be produced by emulsion polymerization, bulk polymerization or suspension polymerization. A polymer produced by suspension polymerization is preferable in consideration of the initial colorability of the fiber.

As the vinyl chloride resin used for the polyvinyl chloride resin fiber used in the present invention, a chlorinated vinyl chloride resin can also be used. As the chlorinated vinyl chloride resin, a vinyl chloride resin is used as a raw material, which is reacted with chlorine to increase the chlorine content to 58 to 72%. Since the heat resistance of the resin increases by chlorinating and increasing the chlorine content, the use of a chlorinated vinyl chloride resin has the effect of suppressing fiber shrinkage. The viscosity average polymerization degree of the chlorinated vinyl chloride resin (viscosity average polymerization degree of the raw vinyl chloride resin) is preferably 300 to 1100. If the viscosity average polymerization degree is less than 300, the heat shrinkage of the fiber Since the effect of lowering the rate is reduced, the fiber has a slightly higher shrinkage rate. On the other hand, when the viscosity average degree of polymerization exceeds 1100, the melt viscosity becomes high, and the nozzle pressure at the time of spinning tends to be high, so that safe operation tends to be difficult. Particularly preferably, the viscosity average degree of polymerization is from 500 to 900. Further, if the chlorine content is less than 58%, the effect of lowering the heat shrinkage rate of the fiber is reduced. Conversely, if the chlorine content exceeds 72%, the melt viscosity tends to be high and stable operation becomes difficult. Absent.

The chlorinated vinyl chloride resin is preferably used in combination with a vinyl chloride resin rather than being used alone in terms of yarn breakage during spinning and coloring of the yarn due to heat. It is preferable to mix the chlorinated vinyl chloride resin at a ratio of 0 to 40% by weight with respect to 100 to 60% by weight of the vinyl chloride resin, and further chlorinated vinyl chloride with respect to 90 to 70% by weight of the vinyl chloride resin. It is preferable to mix the resin at a ratio of 10 to 30% by weight. If the chlorinated vinyl chloride resin exceeds 40% by weight, yarn breakage tends to occur during spinning.

As the stabilizer used for the polyvinyl chloride resin fiber used in the present invention, conventionally known stabilizers can be used. Among them, a tin-based heat stabilizer, a Ca—Zn-based heat stabilizer, a hydrotalcite-based heat stabilizer, At least one heat stabilizer selected from an epoxy heat stabilizer and a β-diketone heat stabilizer is preferred. The heat stabilizer is preferably used in an amount of 0.2 to 5 parts by weight, more preferably 1 to 3 parts by weight. If it is less than 0.2 parts by weight, the effect as a heat stabilizer is poor. Even if it exceeds 5 parts by weight, the thermal stability is not greatly improved, which is economically disadvantageous.

The addition of the heat stabilizer prevents the resin from being thermally decomposed during spinning, so that the color tone of the fiber is not lowered and the spinning can be performed stably (long-run spinnability). The long run spinnability is a property that can be stably operated continuously without stopping the spinning process for several days and can produce fibers. Resin composition with low long-run spinnability can be used to replace breaker plates and nozzles within a relatively short period of time after starting operation, for example, when thread breakage starts due to plate-out or the die pressure starts to rise. Need to restart, production efficiency is poor. The decrease in the color tone of the fiber refers to the initial coloration of the fiber during spinning.

Among the thermal stabilizers, the tin stabilizers include dimethyltin mercapto, dimethyltin mercaptoide, dibutyltin mercapto, dioctyltin mercapto, dioctyltin mercaptopolymer, dioctyltin mercaptoacetate, etc. Examples thereof include maleate tin thermal stabilizers such as maleate, dibutyltin maleate, dioctyltin maleate, and dioctyltin maleate polymer, and laurate tin thermal stabilizers such as dimethyltin laurate, dibutyltin laurate, and dioctyltin laurate. Examples of the Ca—Zn heat stabilizer include zinc stearate, calcium stearate, zinc 12-hydroxystearate, and calcium 12-hydroxystearate. Examples of the hydrotalcite-based heat stabilizer include Alkamizer manufactured by Kyowa Chemical Industry Co., Ltd. Examples of the epoxy heat stabilizer include epoxidized soybean oil and epoxidized linseed oil. Examples of the β-diketone heat stabilizer include stearoylbenzoylmethane (SBM) and dibenzoylmethane (DBM).

Conventionally known lubricants can be used for the polyvinyl chloride resin fibers used in the present invention, and in particular, metal soap lubricants, polyethylene lubricants, higher fatty acid lubricants, ester lubricants, higher alcohol lubricants. At least one selected from the group consisting of The lubricant is effective for controlling the molten state of the composition and the state of adhesion between the composition and a metal surface such as a screw, cylinder or die in the extruder. The lubricant is preferably used in an amount of 0.2 to 5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. More preferably, it is 1 to 4 parts by weight. When the amount is less than 0.2 parts by weight, production efficiency is lowered due to an increase in die pressure and a decrease in discharge amount during spinning, and further, yarn breakage and an increase in nozzle pressure are likely to occur, and stable production becomes difficult. Exceeding 5 parts by weight is not preferable because stable production becomes difficult as in the case of less than 0.2 parts by weight due to a decrease in discharge amount, frequent yarn breakage, and the like, and a transparent fiber tends to be not obtained.

Examples of the metal soap lubricant include metal soaps such as stearate salts such as Na, Mg, Al, Ca, Ba, laurate salts, palmitate salts, and oleate salts. Examples of the higher fatty acid lubricant include saturated fatty acids such as stearic acid, palmitic acid, myristic acid, lauric acid and capric acid, unsaturated fatty acids such as oleic acid, and mixtures thereof. Examples of higher alcohol lubricants include stearyl alcohol, palmityl alcohol, myristyl alcohol, lauryl alcohol, oleyl alcohol, and the like. Examples of ester lubricants include ester lubricants composed of alcohol and fatty acids, pentaerythritol lubricants such as pentaerythritol or monoesters, diesters, triesters, tetraesters, or mixtures thereof of pentaerythritol or dipentaerythritol and higher fatty acids, and montanic acid. Examples thereof include montanic acid wax-based lubricants of esters of stearyl alcohol, palmityl alcohol, myristyl alcohol, lauryl alcohol, oleyl alcohol, and other higher alcohols.

When producing the polyvinyl chloride resin fibers used in the present invention, depending on the purpose, for example, further processing aids, matting agents, fillers, plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, etc. Flame retardants, pigments and the like can be used.

Among these, ethylene-vinyl acetate (EVA) resin for obtaining a soft touch, such as PES-250 manufactured by Nihon Unicar Co., Ltd., and acrylic resin for further improving the extrusion processability, for example, PA-20 manufactured by Kaneka Corporation may be added.

For the polyvinyl chloride resin fiber used in the present invention, a known melt spinning method can be used in the fiberizing step. For example, vinyl chloride resin, chlorinated vinyl chloride resin, heat stabilizer and lubricant are mixed at a specified ratio, stirred and mixed with a Henschel mixer, etc., then filled into an extruder, cylinder temperature 150 to 190 ° C., nozzle In the temperature range of 180 ± 15 ° C., the resin is extruded under conditions with good spinnability, melt spinning is performed, and an undrawn yarn is obtained.

Further, when spinning the undrawn yarn, a conventionally known extruder can be used. For example, a single screw extruder, a different-direction twin screw extruder, a conical twin screw extruder, etc. can be used, but a single screw extruder having a diameter of about 35 to 85 mmφ or a conical extruder having a diameter of about 35 to 50 mmφ is particularly preferable. Good to use. The hole shape of the nozzle used at this time is a shape that approximates the final cross-sectional shape, but the shape dimension slightly changes depending on the die swell or stretching at the time of spinning. . The shape of the nozzle hole is not particularly limited, and is circular, flat oval, glasses, saddle, star, C, H, T, Y, cross, pentagon, hexagon Type, octagonal type, etc. can be selected. Among these, it is desirable that the rigidity does not increase remarkably, and a flat elliptical shape, a spectacle shape, and a saddle shape are preferable, and a spectacle shape and a saddle shape are more preferable.

The extruded filament is heat-treated for about 0.5 to 1.5 seconds in a heated spinning cylinder (under 200-300 ° C atmosphere and good spinnability) provided directly under the nozzle, and the produced undrawn yarn is drawn by a take-up roll. Sent to the process. Next, the undrawn yarn is drawn about 2 to 4 times through a hot air circulation box whose temperature is adjusted to 100 to 130 ° C. between the take-up roll and the drawing roll.

Next, by pulling between two pairs of conical rolls installed in a hot air circulation box whose temperature is adjusted to 110 to 150 ° C, a relaxation treatment of about 20 to 50% is continuously performed, and the multifilament is wound up. The fiber of the present invention is produced. At this time, in order to reduce the shrinkage stress, the heat treatment temperature is desirably high, preferably 120 to 145 ° C., more preferably 130 to 140 ° C. When the heat treatment temperature is lower than 110 ° C., the shrinkage stress at 130 ° C. cannot be sufficiently reduced, so that fiber bending occurs and the commercial property is lowered. When the heat treatment temperature is higher than 150 ° C., the polyalkylene oxide compound is supported. However, it becomes difficult to sufficiently suppress the fusion between the fibers, and the tactile sensation becomes hard.

In order to reduce intramolecular strain, the relaxation rate is desirably as low as possible, preferably 10% or less per minute, and more preferably 8% or less per minute. preferable. When the relaxation rate exceeds 10% per minute, the strain in the fiber cannot be sufficiently removed, so that fiber bending tends to occur due to fiber contraction, and the tactile sensation deteriorates. Further, the relaxation heat treatment time is preferably 2 to 60 minutes, more preferably 4 to 20 minutes. If the heat treatment time is shorter than 2 minutes, it is difficult to make the shrinkage ratio between the multifilaments uniform. If it is longer than 60 minutes, it is difficult to sufficiently suppress the fusion between fibers even if a polyalkylene oxide compound is supported. Becomes hard.

Further, in order to adjust the shrinkage rate, the fiber after the relaxation heat treatment may be further stretched in a range of 0.1 to 4%. Further, in order to release mild interfiber fusion, a nip roll or a refracted portion may be introduced into the process after the relaxation heat treatment.

The fineness of the single fiber constituting the artificial hair fiber of the present invention is preferably 20 to 100 dtex, more preferably 40 to 90 dtex, as in the case of ordinary artificial hair fibers. If it is thinner than 20 dtex, the curl after processing the product becomes weak, and the style is remarkably lowered. On the other hand, if it is thicker than 100 dtex, the rigidity of the fiber becomes high and the tactile sensation becomes hard.

The thermoplastic resin fiber used in the present invention has a Young's modulus of 4 to 9 GPa, a shrinkage rate at 130 ° C. of 10% or less, a composition excluding polyvinyl chloride resin, and a composition ratio in a fiber bundle for artificial hair. Is 0 to 80% by weight.

In the present invention, the thermoplastic resin fiber has a role of preventing the deterioration of the tactile sensation by suppressing the shrinkage of the polyvinyl chloride resin fiber, and is required to have rigidity sufficient to absorb the shrinkage stress. Rigidity can use Young's modulus as an index. The thermoplastic resin fiber in the present invention needs to have a Young's modulus of 4 to 9 GPa, preferably 4.5 to 8 GPa, more preferably 5 to 7 GPa. If the Young's modulus is less than 4 GPa, the effect of suppressing the shrinkage of the polyvinyl chloride resin fibers cannot be sufficiently obtained, and the tactile sensation is deteriorated due to the generation of fiber bending. On the other hand, if the Young's modulus is greater than 9 GPa, the feeling of touch and style are deteriorated because the stiffness of the hair fibers is too strong.

Also, the thermoplastic resin fiber needs to be softened and not deformed at the curl shape imparting temperature, and a shrinkage rate of 130 ° C. can be used as an index thereof. In the measurement of the shrinkage rate in the present invention, a fiber bundle having a total fineness of 15000 to 25000 dtex by bundling single fibers is used, and an average value of 20 times in total is used. At this time, if the fluctuation range of the shrinkage rate is large even in the same fiber, it causes fiber bending. Therefore, when fibers having a shrinkage difference of 2% or more from the average shrinkage occupy 30% or more in the same fiber, there is a possibility that good tactile sensation may not be maintained, so that it is preferable not to use them. The thermoplastic resin fiber used in the present invention needs to have a shrinkage rate at 130 ° C. of 10% or less, preferably 4% or less, more preferably 1% or less. When the shrinkage rate at 130 ° C. is higher than 10%, the effect of suppressing the shrinkage of the polyvinyl chloride resin fibers cannot be sufficiently obtained, and the tactile sensation is deteriorated due to the generation of fiber bending.

The composition ratio of the thermoplastic resin fibers used in the present invention in the fiber bundle for artificial hair is 0 to 80% by weight, preferably 25 to 70% by weight, more preferably 40 to 60% by weight. When the composition ratio in the fiber bundle for artificial hair is higher than 80% by weight, the soft tactile feel and style properties of the polyvinyl chloride resin fiber cannot be sufficiently obtained, and the commercial property is lowered.

The composition of the thermoplastic resin fiber used in the present invention is not particularly limited as long as it is a thermoplastic resin excluding a polyvinyl chloride resin. In the case of a polyvinyl chloride resin fiber, for example, it is possible to increase the rigidity by blending an inorganic substance, but since it has a characteristic that the fiber bending when bending occurs as described above, It is difficult to prevent deterioration of tactile sensation. Specific examples of the composition used for the thermoplastic resin fiber include acrylonitrile resin, modacrylic resin, polyolefin resin, polyester resin, polyamide resin, polyimide resin, polyetherimide resin, and polyamide. Examples include imide resins, polyoxymethylene resins, polyether ketone resins, polycarbonate resins, polysulfone resins, polyether sulfone resins, polyphenylene ether resins, polyferene sulfide fibers, and Teflon (registered trademark) resins. Can be mentioned. Of these, acrylonitrile-based resin, modacrylic resin, polyester-based resin, polyamide-based resin, polycarbonate-based resin, polyethersulfone-based resin, polyphenylene sulfide-based resin, more preferably Modacrylic resins and polyester resins are used. These compositions may be mixed in several kinds, and may be a composite composition fiber having a multilayer structure such as a core-sheath structure.

The thermoplastic resin fiber used in the present invention preferably has a LOI value of 25 or more. The product for hair is required to have flame retardancy for its purpose of use, and a certain flame retardancy can be obtained by mixing a large amount of polyvinyl chloride resin fiber having digestive performance. The present invention is characterized by providing a fiber bundle for artificial hair suitable for supporting a combustible amino-modified silicone compound on a fiber bundle, and the fiber bundle for artificial hair has a high level of flame retardancy. It is desirable. For this reason, it is desirable that the thermoplastic resin fiber also has flame retardancy, and the LOI value is used as an index thereof.

The LOI value of the thermoplastic resin fiber used in the present invention is preferably 25 or more, more preferably 27 or more. If the LOI value is lower than 25, the fiber bundle cannot have sufficient flame retardancy and may ignite and spread. As a means for setting the LOI value to 25 or more, there are a method using a flame-retardant resin such as a modacrylic resin or a polyphenylene sulfide resin, and a method of blending various flame retardants into the resin. The flame retardant that can be used for the thermoplastic resin fiber of the present invention is not particularly limited as long as it does not impair the gloss and hue, and specifically, for example, a phosphorus flame retardant, a bromine-containing polymer, a chlorine-containing polymer, and the like can be used. . In addition, flame retardant aids such as antimony compounds can be used as needed.

The thermoplastic resin fibers used in the present invention may be a mixture of a plurality of different fibers as long as they satisfy the Young's modulus, shrinkage rate, and LOI value of the above conditions. For example, for the purpose of improving the functionality, such as the appearance, tactile sensation, and volume sensation of the fiber bundle for artificial hair, it has surface irregularities such as fibers with a low specific gravity and acrylic synthetic fibers described in International Publication No. WO2005 / 082184. A fiber etc. can be used.

In the present invention, when a fiber bundle in which polyvinyl chloride resin fibers and thermoplastic resin fibers are mixed is processed into a hair product, an amino-modified silicone compound is supported on the fiber bundle surface at 95 to 130 ° C. It is possible to give a curled shape.

The amino-modified silicone compound used in the present invention has a role of expressing a smooth and moisturizing feeling similar to human hair. Furthermore, polyvinyl chloride resin fibers using conventional oil agents that do not contain silicone compounds have the problem that when heated at 95 ° C. or higher, fusion occurs between the fibers and the feel of the hair product becomes stiff. The silicone compound has a role of suppressing the fusion.

The amino-modified silicone compound used in the present invention is an oily compound that is liquid at 23 ° C. in which an imino group or an amino group is present in the side chain of the linear polydimethylsiloxane, and the amino group is adsorbed on the fiber surface. Adheres to the fiber more efficiently than a dimethyl silicone compound, and reduces the surface energy of the fiber to lower the frictional resistance, thereby obtaining a smooth, moisturizing and moisturizing feeling that is preferred by human hair. I can do it. However, if there are too many amino groups in the silicone compound, the surface tension of the oil will increase and the frictional resistance reduction effect will decrease, and the hydrophilicity will increase and the durability will be reduced because it will flow down from the fiber surface due to sweat or rain. Therefore, it is necessary to select an optimal amino group amount. A suitable amine equivalent in the amino-modified silicone compound of the present invention is 1000 to 20000 g / mol, preferably 1250 to 10000 g / mol, more preferably 1500 to 5000 g / mol. When the amine equivalent is lower than 1000 g / mol, the tactile sensation and durability for use are lowered because of too many amine groups, and when the amine equivalent is higher than 20000 g / mol, the amount of adsorption with the fiber is lowered and the tactile sensation is also lowered. The molecular end of the amino-modified silicone compound may be any of a methyl group, a hydroxyl group, and an amino group, and amino-modified silsesquioxane may be added as long as the liquid state can be maintained.

The present invention makes it possible to impart a curl shape at 95 to 130 ° C. by combining polyvinyl chloride resin fibers and thermoplastic resin fibers. By heating at such a high temperature, the amino-modified silicone compound is Adsorption on the fiber surface will be optimized. This further improves the smoothness and drop-off resistance from the fiber surface as compared with the conventional heating at 90 ° C., and improves the tactile sensation and durability of use. However, when the molecular weight of the amino-modified silicone is low, it penetrates into the inside of the fiber and the original modification effect is reduced, so it is necessary to select an optimal molecular weight. Among silicone compounds, silicone oil generally generally has a molecular weight defined by kinematic viscosity, but in the amino-modified silicone compound of the present invention, the preferred kinematic viscosity is 500 to 20000 mm ² / s at 25 ° C., more preferably 1000 to 10000 mm ² / s. When the kinematic viscosity is lower than 500 mm ² / s, the amount of penetration into the fiber increases, so the effect of improving the tactile sensation is not sufficient, and when it is higher than 10000 mm ² / s, it is difficult to uniformly adhere to the fiber surface. Therefore, the tactile sensation improving effect is also reduced.

The method of supporting the amino-modified silicone compound used in the present invention on the fiber is not particularly limited. For example, the emulsion is emulsified with water as a solvent, and then the fiber is immersed and the amount remaining in the fiber is adjusted by centrifugal dehydration. There is a method of carrying on the fiber surface. When preparing an emulsified emulsion using water as a solvent, use a surfactant or the like so that the solid content is 5 to 25%, and neutralize with acetic acid if necessary. . At this time, an antistatic agent or a smoothing agent may be used in combination. Preferable combination components include nonionic surfactants that have a smoothing effect and an antistatic effect and also function as an emulsifying surfactant.

Before dipping the fiber in the emulsion of amino-modified silicone compound, use a surfactant to remove the excess fiber treatment agent adhering to the fiber surface of the polyvinyl chloride resin fiber and thermoplastic resin fiber. May be performed.

The amount of the amino-modified silicone compound used in the present invention supported on the fiber is preferably 0.05 to 0.8 omf%, preferably 0.1 to 0.6 omf%, more preferably 0.2 to 0.4 omf%. When the supported amount to the fiber is less than 0.05 omf%, the effect of improving the tactile sensation is small, and when it is more than 0.8 omf%, the fiber is excessively converged and the volume feeling is lowered to reduce the merchantability. To do.

The fiber bundle for artificial hair of the present invention is characterized by imparting a curl shape at 95 to 130 ° C., and the shrinkage rate of the polyvinyl chloride resin fiber at the temperature is not lower than the shrinkage rate of the thermoplastic resin fiber. And the difference in shrinkage between the polyvinyl chloride resin fiber and the thermoplastic resin fiber is 6% or less.

The method for imparting the curl shape is not particularly limited. For example, the fiber bundle is wound spirally or concentrically on a cylindrical pipe, and is heated by heating at a predetermined temperature for a predetermined time while maintaining the shape. The attached shape is stored in the fiber bundle, and then a method of cooling and removing the fiber bundle from the pipe can be used. The diameter of the pipe at this time can be arbitrarily selected according to the product style, but in the present invention, the thermoplastic resin fibers are in close contact with the polyvinyl chloride resin fibers to form a plurality of fulcrums, and at these fulcrums, polyvinyl chloride is used. By supporting the resin fiber, the effect of suppressing shrinkage is expressed. For this reason, it is necessary to pressure-bond the fiber bundle against the pipe so that each fiber is in close contact, and as a method, a method of squeezing the pipe while maintaining the tension with one end of the fiber bundle fixed to the pipe, You can use a method of spreading it on a pipe using laying paper. In addition to the circular curled shape, it can also be applied to straight straight styles, but in that case, it is necessary to use a method such as binding both ends or sandwiching the whole with a plate in order to bring the fibers into close contact.

When the temperature for imparting the curled shape is increased, the effect of improving the style properties and the effect of improving the feel of amino-modified silicone are amplified. On the other hand, if the temperature is excessively increased, the polyvinyl chloride resin fibers are fused by heat. And feel harder. For this reason, it is necessary to set the temperature in the range of 95 to 130 ° C. in view of the balance between the two, and a preferable temperature is 100 to 120 ° C., more preferably 105 to 115 ° C. When the curl-shaped imparting temperature is lower than 95 ° C., the effect of improving the tactile sensation is not sufficient, and the style is worse than the polyvinyl chloride resin fiber alone because it is lower than the minimum processing temperature of the thermoplastic resin fiber. There is a case. Also, when the curl-shaped imparting temperature is higher than 130 ° C., the polyvinyl chloride resin fiber greatly exceeds the softening temperature, so it becomes difficult to suppress the fusion between the fibers only with the fiber treatment agent, and the tactile sensation becomes hard. Productivity is reduced.

Even within this temperature range, if the shrinkage difference between the polyvinyl chloride resin fiber and the thermoplastic resin fiber is large, the thermoplastic resin fiber bends and the pressure between the fibers decreases, so that the polyvinyl chloride A fiber bending occurs in the resin fiber and the tactile sensation deteriorates. Therefore, the difference between the shrinkage ratio of the polyvinyl chloride resin fiber and the shrinkage ratio of the thermoplastic resin fiber at the curling temperature needs to be 6% or less, preferably 4% or less, more preferably 3% or less. If the difference in shrinkage between the polyvinyl chloride resin fiber and the thermoplastic resin fiber exceeds 6%, the thermoplastic resin fiber is bent and the crimping force between the fibers is reduced, and the polyvinyl chloride resin fiber is bent and touched. Gets worse. The thermoplastic resin fibers may be composed of fibers having a plurality of compositions, but the fibers having any composition must satisfy the above shrinkage relationship.

Hereinafter, specific examples of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Experimental example 1) Shrinkage Before each fiber was mixed, or single fibers of one material were selected and bundled from the mixed fiber bundle, and a fiber bundle having a total fineness of 18000 ± 3000 dtex was produced. The fiber bundle is cut to a length of 40 cm, marked at a position of 5 cm from both ends, with only one end fixed, heated at a predetermined temperature for 30 minutes under drying conditions, and cooled at room temperature. went. The length between the markings of the fiber bundle after cooling was measured, and the shrinkage was determined from the ratio to the original length of 30 cm. This measurement was performed 20 times in total, and the average value was taken as the shrinkage rate of the sample. Since the sample may be shorter than 40 cm in an actual hair product, the length between the markings can be shortened according to the length that can be sampled.

(Experimental example 2) Oil agent carrying amount After taking out the fiber from the fiber bundle and measuring the weight, it was immersed in a mixed solvent of ethanol / cyclohexane = 50% / 50% for 20 minutes, and after removing the fiber from the mixed solvent, the mixed solvent was added. The mixture was heated and vaporized at 120 ° C., and the weight of the remaining compound that was not vaporized was measured. Based on this value, the amount carried on the fiber was determined by the following equation. Compound remaining weight / (fiber weight−compound remaining weight) × 100 = the amount of compound supported on the fiber surface (omf%).

(Experimental example 3) Young's modulus Using a Tensilon universal testing machine (RTC-1210A) manufactured by A & D Co., Ltd., the value of Young's modulus was determined from the stress-strain curve under the condition of a tensile speed of 20 cm / min. The average value was taken as the Young's modulus of the sample.

(Experimental example 4) Shrinkage stress The thermal contraction stress of the fiber was measured using SSC5200H thermal analysis TMA / SS150C by Seiko Electronics Industry. Take 10 monofilaments of 10 mm in length, apply a load of 336.2 mN, measure the shrinkage stress in the range of 30-240 ° C at a heating rate of 5 ° C / min, and measure the value of the shrinkage stress at 130 ° C The number of fibers was divided by 10 to obtain the shrinkage stress of one single fiber, and further divided by the fineness of the single fiber to obtain the shrinkage stress (μN / dtex) per unit fineness.

(Experimental example 5) LOI (limit oxygen index)
A filament of 16 cm / 0.25 g was weighed, the ends were lightly collected with double-sided tape, and sandwiched and twisted with a suspender. When the twist was sufficiently applied, the middle of the sample was folded in two and the two were twisted together. The ends were fastened with cellophane tape so that the total length was 7 cm. Pre-drying was performed at 105 ° C. for 60 minutes, and further drying was performed for 30 minutes or more with a desiccator. The dried sample was adjusted to a predetermined oxygen concentration, and after 40 seconds, it was ignited from the top with an igniter throttled to 8 to 12 mm, and the igniter was released after ignition. The oxygen concentration that burned 5 cm or more or continued burning for 3 minutes or more was examined, and the test was repeated three times under the same conditions to obtain the critical oxygen index.

(Experimental example 6) Productivity: smoothness A single fiber is extracted and allowed to stand on a horizontal plate under no load, and the shape is captured as a digital image. The angle is less than 170 ° with 20 cm × 8 fibers per sample. The number of fiber bends was counted and the number of fiber bends per meter was determined. Further, in a sample in which a plurality of materials were mixed, after counting the number of fiber bends of each material, the number of fiber bends as a fiber bundle was obtained by multiplying the composition ratio. Together with the number of fiber bends, fiber smoothness was determined in the following five stages based on the evaluation of general engineers engaged in beauty evaluation such as wigs, and a level of 3 or more points was accepted.
5 points: less than 10 bends / m of fiber bending: very good tactile feeling with no feeling of roughness 4 points: More than 10 bends / m of fiber bend, less than 20 points / m: good tactile feeling without feeling of bend 3 points: Fiber bending number of 20 / m or more and less than 50 / m: Feeling slightly gritty, but tactile sensation of a level applicable as a product: 2 points: Fiber bending number of 50 / m or more, less than 100 / m: Feeling gritty Therefore, one point of tactile sensation that is difficult to apply as a product: 100 or more fiber bends / m: A tactile sensation that is extremely rough and cannot be applied to a product.

(Experimental example 7) Productivity: softness About a fiber bundle for artificial hair, a general engineer engaged in beauty evaluation of wigs and the like evaluates the appearance in five stages based on reproducibility of soft touch close to human hair. And a score of 3 or more was accepted.
5 points: soft and good tactile feeling almost equivalent to human hair 4 points: soft tactile feeling close to human hair 3 points: Although somewhat hard, tactile feel relatively close to human hair 2 points: Hardness peculiar to synthetic fibers Feeling of touch 1 point: Tactile sensation that is clearly different from human hair, in which some interfiber fusion remains.

(Experimental example 8) Productivity: moisturizing / moisturizing feeling A general engineer engaged in beauty evaluation of wigs and the like with respect to a fiber bundle for artificial hair, based on whether it has a moisturizing feeling or moisturizing feeling close to human hair. Appearance was evaluated in stages, and a level of 3 or more was accepted.
5 points: good feeling of moisture and moisturizing feeling close to human hair 4 points: slightly dull, but moisturizing and moisturizing feeling close to human hair 3 points: moist feeling Although one of the moisturizing sensations is inadequate, tactile sensation at a level relatively close to human hair 2 points: moist feeling, moisturizing feeling clearly inferior to human hair 1 point: moist feeling, moisturizing sensation recognized Tactile feeling that can not be done.

(Experimental Example 9) Productivity: Elasticity / Curl Shape Stability Regarding a fiber bundle for artificial hair, the fiber bundle is hung for 60 hours after imparting the curl shape, and a general engineer engaged in beauty evaluation such as wigs gives elasticity Based on whether the curl shape is maintained even after long-term use, stability was determined in five stages, and a level of 3 or more points was accepted.
5 points: When the sample is moved, the curl jumps pulsating without any sense of incongruity, and the curl shape is almost undisturbed. State 3 point: When the sample is moved, the curl is slightly weak and the curl shape is somewhat disturbed. 2 point: When the sample is moved, the curl is in a suspended state, and the curl shape is greatly disturbed 1 Point: A state in which the curl is stretched and greatly disturbed before it is moved only by holding for 60 hours.

(Experimental example 10) Productivity: Sense of volume About a fiber bundle for artificial hair, a general engineer engaged in cosmetic evaluation of wigs, etc. has a volume in five stages based on the appearance of the fiber bundle sample and the repulsive force when clasped. The feeling was judged, and a level of 3 or more points was accepted.
5 points: Excellent bulkiness in appearance and repulsion even with the same weight based on 3 points 4 points: Slightly higher bulkiness with the same weight based on 3 points 3 points: Standard level 2 points: 3 Bulkiness is slightly inferior at the same weight based on the point 1 point: Bulkiness is clearly inferior at the same weight based on the 3 points.

(Experimental example 11) Productivity: Comprehensive evaluation Smoothness, softness, moisturizing feeling / moisturizing feeling, elasticity feeling / curl shape stability, and a sense of volume are added together, and 21 points or more are excellent. 17 points were judged good, 16-14 points were averaged, 13 points or less were judged as inferior, and good or better were judged as acceptable.

(Production Example 1) PVC-1
10 parts by weight of chlorinated polyvinyl chloride resin H438 (manufactured by Kaneka Corp.) and 100 parts by weight of polyvinyl chloride resin S1001 (manufactured by Kaneka Corp.), hydrotalcite heat manufactured by Kyowa Chemical Co., Ltd. 1 part by weight of Alkamizer 1 as a stabilizer, 0.5 parts by weight of EW-100 manufactured by Riken Vitamin Co., Ltd. as an ester lubricant, and HW400P manufactured by Mitsui Chemicals Co., Ltd. as a polyethylene wax type Add 5 parts by weight, 0.4 parts by weight of β-diketone, 0.4 parts by weight of calcium soap / zinc soap, and 2 parts by weight of epoxidized soybean oil, and stir and mix with a Henschel mixer to produce a compound. did. A black pigment was added for color adjustment. 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. The hole shape was a saddle shape. The above compound was extruded and melt-spun in the 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, a nonionic surfactant (polyethylene oxide / polypropylene oxide copolymer, molecular weight of about 800), cationic surfactant (ammonium sulfate compound, molecular weight of about 800): ester oil (olein) An oil agent consisting of oleyl acid (molecular weight: about 500) was attached so as to be 0.5 omf% with respect to the fiber. Next, it extended | stretched about 3 times through the 110 degreeC hot-air circulation box between 2nd extending | stretching rolls. Furthermore, it is drawn between two pairs of conical rolls installed in a box whose temperature is adjusted to 110 ° C., and is subjected to a relaxation heat treatment of about 35% in 2 minutes, so that the single fibers therein have a fineness of about 77 to 81 dtex. The multifilament was wound around to prepare polyvinyl chloride resin fiber PVC-1.

(Production Example 2) PVC-2
The component of the oil agent is a polyethylene oxide / polypropylene oxide copolymer having a molecular weight of 10,000, the amount of oil agent attached is 0.2 omf%, the temperature of the relaxation heat treatment is 130 ° C., and the relaxation rate is 35% relaxation for 4 minutes. In the same manner as in Production Example 1, a polyvinyl chloride fiber PVC-2 was produced.

(Production Example 3) PVC-3
A polyvinyl chloride fiber PVC-3 was produced in the same manner as in Production Example 2 except that the relaxation rate was reduced to 37% over 6 minutes.

(Production Example 4) PVC-4
A polyvinyl chloride fiber PVC-4 was produced in the same manner as in Production Example 2, except that the relaxation rate was reduced to 39% over 8 minutes.

(Production Example 5) PVC-5
The components of the oil agent include nonionic surfactant (polyethylene oxide / polypropylene oxide copolymer, molecular weight of about 800), cationic surfactant (ammonium sulfate compound, molecular weight of about 800): ester oil (oleyl oleate: A polyvinyl chloride fiber PVC-5 was produced in the same manner as in Production Example 3 except that the molecular weight was about 500) and the amount of oil attached was 0.5 omf%.

(Production Example 6) PVC-6
The component of the oil was 75% by weight of polyethylene oxide / polypropylene oxide copolymer having a molecular weight of 10,000, 25% by weight of amino-modified silicone oil having a kinematic viscosity of 1000 mm ² / S, and the amount of oil attached was 0.2 omf%. Using a method similar to that in Production Example 3, polyvinyl chloride fiber PVC-6 was produced.

(Production Example 7) TPR-1
An acrylic copolymer resin obtained by copolymerizing 50% acrylonitrile, 49% vinyl chloride, and 1% sodium styrenesulfonate was dissolved in acetone to prepare a 29% spinning dope. This spinning stock solution was spun into a 20% aqueous acetone solution at 20 ° C. using a dumbbell shaped cross-section nozzle under a nozzle draft of 1.6, and the resulting fiber was desolvated in a water washing bath at 50 ° C. and 1. The film was stretched 5 times, then dried dry at 130 ° C., then stretched 2.5 times at 125 ° C., and further subjected to relaxation heat treatment at 150 ° C. dry heat. The single fiber fineness of the acrylic fiber thus obtained was 47 dtex. The cross-sectional shape was substantially a horseshoe shape.

(Production Example 8) TPR-2
100 parts by weight of polyethylene terephthalate (manufactured by Mitsubishi Chemical Corporation, BK-2180), brominated flame retardant (manufactured by Sakamoto Pharmaceutical Co., Ltd., SR-T20000), antimony compound (manufactured by Nippon Seiko Co., Ltd., SA-A) ) Is dried to a water content of 100 ppm or less, and then 2 parts of polyester pellets for coloring PESM6100 BLACK (manufactured by Dainichi Seika Kogyo Co., Ltd., carbon black content 30%) are added, dry blended, and supplied to a twin screw extruder. After melt-kneading at 280 ° C. and pelletizing, it was dried to a water content of 100 ppm or less. Next, at 280 ° C. with a melt spinning machine, using a spectacle-type nozzle, the molten polymer is discharged from the spinneret and cooled in a water bath at a water temperature of 50 ° C. set at a position 30 mm below the base, at a speed of 100 m / min. The unwound yarn was obtained by winding. The obtained unstretched yarn is stretched in a warm water bath at 80 ° C. to obtain a 4-fold stretched yarn, wound at a speed of 100 m / min using a heat roll heated to 200 ° C., heat treated, and single fiber A polyester fiber (multifilament) having a fineness of around 65 dtex was obtained.
The physical properties of the fibers obtained in Production Examples 1 to 8 are shown in Table 1.

(Examples 1 to 14, Comparative Examples 1 to 6)
Polyvinyl chloride fibers (PVC-1 to 6) prepared in Production Examples 1 to 8 and thermoplastic resin fibers (TPR-1 and 2) are mixed at the ratio shown in Table 2 to hack and artificial hair fibers It was a bunch. Next, amino-modified silicone oil (by Toray Dow Corning Co., Ltd., BY16203, kinematic viscosity 2000 mm ² / S, functional group equivalent 1900 g / mol), polyethylene oxide / polypropylene oxide copolymer having a molecular weight of 10,000, and pure water by weight The mixture was mixed at a ratio of 0.5: 0.5: 9, stirred with a homogenizer to make an emulsion, and then neutralized by adding acetic acid to prepare a fiber treatment agent. The fiber bundles of Examples 1 to 5, 7 to 13 and Comparative Examples 2, 4, and 6 are immersed in this fiber treatment agent for 5 minutes, and then a centrifugal dehydrator is used so that the supported amount on the fiber surface is 0.4 omf%. After removing the excess fiber treating agent, the fiber bundle was divided into two fiber bundles so that each would have 1.2 million dtex. Similarly, the fiber bundle that did not carry the fiber treatment agent was divided into two fiber bundles so that each would be 1.2 million dtex. Next, one fiber bundle was cut into a length of 35 cm, and 5 cm at both ends were bound with a string, followed by heating at the temperature shown in Table 2 for 1 hour, and the number of fiber bends of the contracted fiber bundle was measured. Next, the remaining fiber bundle is sewed with a wig sewing machine to make a mino hair having a test length of 25 cm, wound on a pipe having a diameter of 35 mm, and heat-set for 1 hour at the temperature shown in Table 2 with a convection dryer. To give a curl shape. This curled mino hair is sewn on the net in 10 steps at 1 cm intervals to produce a product sample, and merchantability (smoothness, softness, moisturizing / moisturizing, elasticity / curl shape stability, volume) Was evaluated. The results are shown in Table 2.

As is apparent from Table 2, the artificial hair fiber of the present invention has excellent tactile sensation and styling properties, and has a quality that greatly exceeds that of conventional products by combining with a particularly rigid fiber, application of a silicone oil agent, application of high-temperature curl, and the like. It was confirmed that it was obtained.

1. Conventional PVC fiber PVC-1
2. Invention PVC fiber PVC-2
3. Invention PVC fiber PVC-3
4). Invention PVC fiber PVC-4

Claims (16)

1. A polyvinyl chloride resin fiber having a shrinkage stress at 130 ° C. of 70 μN / dtex or less.
2. The polyvinyl chloride resin fiber according to claim 1, wherein the shrinkage stress at 130 ° C is 50 µN / dtex or less.
3. The polyvinyl chloride resin fiber according to claim 2, wherein the shrinkage stress at 130 ° C is 40 µN / dtex or less.
4. The polyvinyl chloride resin fiber is a homopolymer resin of vinyl chloride, a copolymer resin of vinyl chloride and vinyl esters, a copolymer resin of vinyl chloride and acrylates, a copolymer resin of vinyl chloride and olefins, and The polyvinyl chloride resin fiber according to any one of claims 1 to 3, which is a resin fiber made of one or more resins selected from the group consisting of vinyl chloride-acrylonitrile copolymer resins.
5. The polyvinyl chloride resin fiber according to any one of claims 1 to 4, wherein the polyvinyl chloride resin fiber is a polyvinyl chloride resin fiber for artificial hair.
6. An artificial hair comprising 20 to 100% by weight of the polyvinyl chloride resin fiber according to any one of claims 1 to 5 and 0 to 80% by weight of a thermoplastic resin fiber having a composition excluding the polyvinyl chloride resin. Fiber bundle.
7. The fiber bundle for artificial hair according to claim 6, wherein the Young's modulus of the thermoplastic resin fiber is 4 to 9 GPa.
8. The fiber bundle for artificial hair according to claim 6 or 7, wherein the shrinkage rate of the thermoplastic resin fiber at 130 ° C is 10% or less.
9. 9. The artificial hair according to claim 6, wherein the shrinkage rate of the polyvinyl chloride resin fiber at 130 ° C. is not lower than the shrinkage rate of the thermoplastic resin fiber at 130 ° C. 9. Fiber bundle.
10. The fiber bundle for artificial hair according to claim 9, wherein the difference between the shrinkage rate of the polyvinyl chloride resin fibers at 130 ° C and the shrinkage rate of the thermoplastic resin fibers at 130 ° C is 6% or less. .
11. The thermoplastic resin fibers are acrylonitrile resin, modacrylic resin, polyolefin resin, polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polyamideimide resin, polyoxymethylene resin, polyether. It consists of one or more resins selected from the group consisting of ketone resins, polycarbonate resins, polysulfone resins, polyether sulfone resins, polyphenylene ether resins, polyferene sulfide fibers, and Teflon (registered trademark) resins. The fiber bundle for artificial hair according to any one of claims 6 to 10, which is a resin fiber.
12. The fiber bundle for artificial hair according to any one of claims 6 to 11, wherein the polyvinyl chloride resin fiber and the thermoplastic resin fiber contain an amino-modified silicone compound.
13. The fiber bundle for artificial hair according to any one of claims 6 to 12, wherein the polyvinyl chloride resin fiber contains 0.07 to 0.5 omf% of a polyalkylene oxide compound having a weight average molecular weight of 2000 to 25000.
14. The artificial hair fiber bundle according to any one of claims 6 to 13, wherein the polyvinyl chloride resin fiber contains 0 to 0.5 omf% of a silicone compound.
15. An artificial hair product obtained by processing the fiber bundle for artificial hair according to any one of claims 6 to 14.
16. The artificial hair product according to claim 15, wherein the processing is performed at 95 to 130 ° C.

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