KR100861058B1 - Flame-retardant polyester fiber for artificial hair - Google Patents

Abstract

In addition to maintaining fiber properties such as heat resistance and elongation, which are the features of polyester fibers, the present invention satisfies the required performance as artificial hair such as ease of setting, setting retention, and the like. Provided is a fiber for artificial hair, which has been provided with drip resistance and flame retardancy, which has not been found in hair fiber. The fiber for artificial hair of the present invention withstands iron setting at least at 180 ° C, has heat resistance at 5% or less of heat shrinkage at 200 ° C, has flame retardancy with a limiting oxygen index (LOI) of 25 or more, and Curls in all temperature ranges from 80 ° C to 200 ° C are possible, and polyester-based artificial fibers have a curling elongation of 35% or less when the curled fibers are left at 25 ° C for 7 days. It is hair fiber.

Frical setting, polyester, polyarylate, drip resistance

Description

Flame retardant polyester fiber for artificial hair {FLAME-RETARDANT POLYESTER FIBER FOR ARTIFICIAL HAIR}

The present invention relates to a polyester-based artificial hair fiber having excellent setting ease, setting retention, heat resistance, drip resistance, and flame retardancy.

Fibers composed of polyethylene terephthalate or polyester mainly composed of polyethylene terephthalate have high melting point, high elastic modulus, excellent heat resistance and chemical resistance, so curtains, rugs, medical care, blankets, sheet paper, tablecloths, chair covers and closets It is widely used in ashes, artificial hairs, automotive interior materials, outdoor reinforcements, safety nets, and the like.

In hair products such as wigs, hair wigs, hair extensions, hair bands, and doll hairs, conventional hairs and artificial hairs as modacryl, polyvinyl chloride and poly Amides, polyesters and the like have been used. The provision of human hair becomes difficult, and the importance of an artificial hair is increasing. Modacrylic or polyvinyl chloride has been used in particular in terms of workability according to each style characteristic of curl or straight, having a suitable feel and feel as an artificial hair material. These materials had the characteristics of flame retardancy as materials, but all were insufficient in terms of heat resistance temperature.

The various hair products described above not only have material properties such as heat resistance and flame retardancy, but also have to combine beauty, design, and commercial properties, and are required to be processed in a curl style in addition to a straight style. This includes a heat setting method of fixing the shape by cooling after imparting a curl shape to the hair raw material in a heated state by using a heat source of dry heat or wet heat in the process of manufacturing or post-processing artificial hair fibers as a pre-curl setting. Generally used.

Even in polyesters having relatively high heat resistance, similar to low heat resistance modacryl, polyvinyl chloride, and the like, it is preferable to perform the frical setting at a relatively low temperature in view of operability and cost effectiveness, and at a temperature of about 80 to 120 ° C. Walking is common.

At the same time, hair iron products such as hair wigs and hair accessories, especially weaving, may be used after being curled after being attached to the hair. The heat setting by) is used a lot. Since this hair iron is generally used when curling human hair, it is used at high temperature around 150 degreeC-180 degreeC. Moreover, among hair irons, since the operation becomes cumbersome in the case of the iron with a code which can control a temperature, the stove type hair iron is used in many cases. This stove-type hair iron uses the heat source of the hair iron heated in the stove as a source of heat, but the temperature of the hair iron becomes remarkable when taken out of the stove, so the temperature in the stove is always kept at a high temperature. It needs to be placed. For this reason, the temperature control of the hair iron at the time of setting tends to be neglected, and it may be used at higher temperature than the said temperature.

As a result, when artificial hair made of synthetic fibers having low heat resistance is used as a product for such a use, when the heat setting is performed by a hair iron, the synthetic fiber is shrunk by shrinkage or heat by a high temperature hair iron. Deformation and, moreover, fusion, make the appearance of the product unsightly.

For this reason, it is preferable that the fiber for artificial hair can be curled at a relatively low temperature, and at the same time, curl setting at a high temperature using a hair iron is possible. While polyester fiber is excellent in heat resistance, as its polymer property, it is harder than the modacryl fiber or polyvinyl chloride fiber, and tends to be more artificial, i.e., unnatural in touch and feel.

In order to improve these problems, a method of adding a relatively flexible component, such as polybutylene terephthalate, to polyethylene terephthalate, for example, is often used as a raw material polymer structure. This method improves the feel and feel and at the same time enables curl setting at lower temperatures. At the same time, however, the flame retardancy and the heat resistance are lowered.

As described above, artificial hair fibers using polyester-based fibers, which are represented mainly by polyethylene terephthalate having excellent heat resistance as compared with the modacryl and polyvinyl chloride, have recently been proposed. However, since polyester fiber is a combustible material, flame retardancy was inadequate.                         

Various attempts have been made to improve the flame retardancy of polyester fibers. For example, a method of copolymerizing a flame retardant monomer containing a phosphorus atom in a polyester resin, a method of containing a flame retardant in a polyester fiber, and the like. This is known. As a method of copolymerizing the former flame retardant monomer, Japanese Unexamined Patent Application Publication No. 55-41610, for example, contains a phosphorus valence ring structure and copolymerizes a phosphorus compound having good thermal stability, and Japanese Unexamined Patent Application Publication 53 JP-A-13479 discloses a method of copolymerizing carboxyphosphinic acid, and Japanese Patent Application Laid-Open No. 11-124732 proposes a method of blending or copolymerizing a phosphorus compound with a polyester containing polyarylate.

As a method of containing the latter flame retardant, Japanese Unexamined Patent Publication No. 3-57990 contains a halogenated cycloalkane compound of fine particles in a polyester fiber, and Japanese Unexamined Patent Application Publication No. 1-24913 describes a bromine atom-containing alkylcyclopeptide. A method of containing hexane and the like have been proposed.

As these flame-retardant techniques applied to artificial hairs, polyester fibers obtained by copolymerizing a phosphorus compound, for example, in Japanese Patent Application Laid-Open No. 3-27105, Japanese Patent Application Laid-Open No. 5-339805, and the like have been proposed. However, since artificial hair is required to have high flame retardancy, in order to use these copolyesters in artificial hair, the copolymerization amount must be increased. As a result, the heat resistance of the polyester is greatly reduced, resulting in melt spinning. Becomes difficult, or when a flame approaches, it does not ignite and burn, but a problem arises that it melts and drips.                         

On the other hand, in the method of containing a flame retardant in a polyester fiber, in order to obtain sufficient flame retardancy, it is necessary to make the containing treatment temperature high temperature 150 degreeC or more, or it is necessary to make the containing treatment time long, or to use a large amount of flame retardants There is a problem that a problem arises such as a decrease in fiber properties, a decrease in productivity, and an increase in manufacturing cost.

Thus, in addition to the physical properties of conventional polyester fibers, flame retardancy, drip resistance, and high temperature, such as 160-200 ° C., which are in the same degree as human hair, which are inherently flame retardant, drip resistance, and difficult to be compatible with polyester fibers. The phenomenon is that artificial hairs with heat resistance that can be thermally set at have not been obtained yet.

An object of the present invention is to maintain fiber properties such as heat resistance and elongation, and to have excellent setting properties at low temperature and high temperature, and to have flame retardancy and drip resistance in addition to the conventional problems. It is to provide a flame-retardant polyester-based artificial hair fibers that did not ever.

As a result of earnestly examining in order to solve the said subject, it discovered that the polyester fiber which has a polyethylene terephthalate as a main component can obtain the fiber which can satisfy all the characteristics required for artificial hair.

Specifically, the composition obtained by melting and kneading at least one polymer selected from the group consisting of polyarylate, polycarbonate, and polyamide, a flame retardant, and a phosphite compound to a polyester mainly composed of polyethylene terephthalate The above object can be attained, or at least one polymer selected from the group consisting of polyarylates, polycarbonates, and polyamides in polyester mainly composed of thermoplastic copolymerized polyethylene terephthalate copolymerized with a reactive phosphorus flame retardant The above object was achieved by fiberizing a composition obtained by melt-kneading a phosphite-based compound with the present invention.

That is, the present invention is for polyester-based artificial hairs that withstands iron setting at at least 180 ° C, has heat resistance of 5% or less in heat shrinkage at 200 ° C, and has flame retardancy with a limiting oxygen index (LOI) of 25 or more. It is about a fiber.

Curl | Karl setting in the temperature range of 80 degreeC-200 degreeC of the said polyester-type artificial hair fiber is possible, and it is preferable that the curl elongation rate when the curled fiber is left still at 25 degreeC for 7 days is 35% or less.

It is preferable that the melt viscosity of the resin composition which comprises the said polyester-type artificial hair fiber is 50-300 Pa.sec at a shear rate of 600 sec ^-1 and a temperature of 280 degreeC.

It is preferable that melting | fusing point of the resin composition which comprises the said polyester-type artificial hair fiber is 250 degreeC or more.

It is preferable that polyalkylene terephthalate is 70 weight% or more in the polymer component in the resin composition which comprises the said polyester-type artificial hair fiber.

It is preferable that the said polyalkylene terephthalate is at least 1 sort (s) chosen from the group which consists of a polyethylene terephthalate, a polypropylene terephthalate, and a polybutylene terephthalate.

The polyalkylene terephthalate may be a thermoplastic copolymerized polyalkylene terephthalate copolymerized with a reactive phosphorous flame retardant.

It is preferable to contain at least 1 sort (s) chosen from the group which consists of polyarylate, polyamide, and polycarbonate as another polymer component in the resin composition which comprises the said polyester-type artificial hair fiber.

As another polymer component in the resin composition which comprises the said polyester-type artificial hair fiber, it is preferable to contain 10 to 30 weight% of polyarylates.

Moreover, it is preferable that the resin composition which comprises the said polyester-type artificial hair fiber contains 1-20 weight part of flame retardants with respect to 100 weight part of polymer components total.

It is preferable that the said flame retardant is phosphorus type | system | group, and contains 0.05-15 weight% with respect to a polymer component in conversion of phosphorus atomic weight.

It is preferable that the resin composition which comprises the said polyester-type artificial hair fiber contains 0.05-5 weight part of antioxidants with respect to 100 weight part of polymer components total.

It is preferable that the said antioxidant is a phosphite system.

It is preferable that the short fiber fineness of the said polyester-type artificial hair fiber is 30-70 dtex.

The polyester-based artificial hair fibers of the present invention withstand heat setting at least at 180 ° C, have heat resistance of 5% or less in heat shrinkage at 200 ° C, and have a limiting oxygen index (LOI) of 25 in the combustion test. It is a fiber for artificial hair having the above flame retardancy.

More preferably, curl setting in all temperature ranges of 80 degreeC-200 degreeC is possible, The curl elongation rate when the curled fiber is left to stand at 25 degreeC for 7 days is 35% or less, More preferably, 27% or less It is a fiber for artificial hair. Curling setting in all the temperature range of 80 degreeC-200 degreeC mentioned here is possible to set pre-curl even at low temperature of about 80 degreeC-100 degreeC, and heat resistance which can endure high temperature of about 180 degreeC-200 degreeC It means that iron setting at high temperature is possible.

The thermal contraction rate at 200 degrees C of the polyester fiber of this invention is 5% or less, Preferably it is 3% or less. If the shrinkage at 200 ° C. is greater than 5%, the shrinkage at the time of iron setting at high temperature tends to shorten or shrink the dimension.

Moreover, the limit oxygen index (LOI) of the polyester fiber of this invention is 25 or more, Preferably it is 27 or more. If the limiting oxygen index is less than 25, it is not sufficient for the flame retardation of the fiber, and it is not a level that safely extinguishs even in the actual combustion behavior of the product. It is preferable that the polyester fiber of this invention consists of a resin composition of 50-300 Pa.sec of melt viscosity at a shear rate of 600 sec ^-1 and a temperature of 280 degreeC, and more preferable melt viscosity is the range of 50-240 Pa.sec. If the melt viscosity is less than 50 Pa sec, melt spinning becomes difficult, and a fiber of stable physical properties cannot be obtained, and a problem arises that the flame easily approaches and burns when the flame approaches or burns the finished hair product. . Moreover, when melt viscosity exceeds 300 Pa.sec, melt resin viscosity becomes too high and melt spinning becomes difficult, and it is difficult to obtain a fiber stably.

In addition, in order to suitably maintain the hot workability at high temperature, that is, the high temperature curl setting property using the hair iron or the like, the melting point is preferably composed of a resin composition having a melting point of 250 ° C or higher, and more preferably 255 ° C or higher.

The polyester-based hair fiber of the present invention is mainly composed of polyester, and is not particularly limited as long as it has the properties as described above, but is preferably copolymerized polyester mainly composed of polyalkylene terephthalate or polyalkylene terephthalate ( Hereinafter, at least one polymer selected from the group consisting of a polymer (A), a polyarylate (B1), a polycarbonate (B2), or a polyamide (B3) (hereinafter referred to as a polymer (B)). It is preferable that the composition obtained by melt-kneading by adding a flame retardant (C) and a phosphite type compound (D) to) is fiberized.

Alternatively, the composition obtained by adding the phosphite compound (D) to the thermoplastic copolymer polyalkylene terephthalate copolymerized with a reactive phosphorus flame retardant as the polymer (A) and the polymer (B) and melt kneading the fiber is obtained. Also good.

It is preferable that the polymer (A) used by this invention is co-polyester mainly having polyalkylene terephthalate and / or polyalkylene terephthalate.

Examples of the polyalkylene terephthalate include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate and the like. Among these, polyethylene terephthalate is more preferable at a heat resistant point.                     

Copolymerized polyester mainly composed of polyalkylene terephthalate is copolymerized polyester containing the polyalkylene terephthalate as a main component and a small amount of copolymerized components. Here, a main component means the case where polyalkylene terephthalate is 80 mol% or more in a polymer (A). As a copolymerization component, polyhydric acids, such as isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, trimellitic acid, pyromellitic acid, succinic acid, glutaric acid, adipic acid, sperinic acid, azeline acid, sebacic acid, dodecaneic acid, etc. Dicarboxylic acids and derivatives thereof, including sulfonic acid salts such as carboxylic acid and derivatives thereof, 5-sodium sulfoisophthalic acid and 5-hydroxysulfoisophthalic acid dihydroxyethyl, 1,2-propanediol, 1,3-propanediol , 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, polyethylene glycol, trimethylolpropane, pentaerythritol, 4-hydroxybenzoic acid, ε-capro Lactone, etc. are mentioned. However, it is not limited to these.

The copolymerized polyester of the said polymer (A) may polycondense the said copolymerization component by a well-known method in the main chain and / or the side chain of the polyalkylene terephthalate which becomes a main body.

The polymer (A) is preferably at least one mixture selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate and copolyester. Moreover, since there exists a tendency for the heat resistance of the fiber obtained when content of polybutylene terephthalate is high here, it is more preferable to set it as 30 weight% or less in all the polymer components.                     

Moreover, it is preferable that these polyalkylene terephthalates are 70 weight% or more in a polymer whole component, More preferably, it is 80 weight% or more. When polyalkylene terephthalate is less than 70 weight%, there exists a tendency for heat resistance to fall.

0.5-1.4 is preferable and, as for the intrinsic viscosity of the said polymer (A), 0.6-1.2 are more preferable. If the intrinsic viscosity is less than 0.5, the mechanical strength of the fiber obtained is lowered, and if it exceeds 1.4, the melt viscosity increases with increasing molecular weight, and melt spinning becomes difficult or the fineness tends to be uneven.

In the present invention, as the polymer (A), a thermoplastic copolymer polyalkylene terephthalate copolymerized with a reactive phosphorous flame retardant can be used. The thermoplastic copolymer polyalkylene terephthalate copolymerized with the reactive phosphorus flame retardant used in the present invention is a copolymer obtained by polycondensing an aromatic dicarboxylic acid or its ester forming derivative, glycol or its ester forming derivative and the reactive phosphorus flame retardant. Refers to polyester.

Examples of the aromatic dicarboxylic acid or its ester-forming derivatives include dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid and derivatives thereof, 5-sodium sulfoisophthalic acid and 5-sodium sulfoisophthalic acid. And dicarboxylic acids and derivatives thereof including sulfonate salts such as dihydroxyethyl. However, it is not limited to these.

Examples of the glycol or ester-forming derivative thereof include 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentylglycol, 1,4-cyclohexanedimethanol, di Ethylene glycol, polyethylene glycol, and derivatives thereof. However, it is not limited to these.

Further, polycarboxylic acids such as trimellitic acid, pyromellitic acid, succinic acid, glutaric acid, adipic acid, sperinic acid, azeline acid, sebacic acid, and dodecaneic acid as components capable of a small amount of copolymerization with the dicarboxylic acids and glycols And derivatives thereof, trimethylolpropane, pentaerythritol, 4-hydroxybenzoic acid, ε-caprolactone and the like.

The reactive phosphorus flame retardant may be used as long as it can be copolymerized with the dicarboxylic acids and glycols. Examples thereof include diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate and 2-methacryl. Loyloxyethyl acid phosphate, diphenyl-2-methacryloyloxyethyl phosphate, tris (3-hydroxypropyl) phosphine, tris (4-hydroxybutyl) phosphine, tris (3-hydroxypropyl) Phosphorus-containing organic compounds such as phosphine oxide, tris (3-hydroxybutyl) phosphine oxide and 3- (hydroxyphenylphosphinoyl) propionic acid, and derivatives thereof; and the like, and these may be used alone or in combination of two or more thereof. You may use it.

The amount of the reactive phosphorous flame retardant added is 0.01 to 8 parts by weight, more preferably 0.05 to 5 parts by weight, still more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the thermoplastic polyester. If the added amount is less than 0.01 part by weight, it is difficult to obtain a flame retardant effect, and when it is more than 8 parts by weight, mechanical properties are impaired. For the production of thermoplastic copolymerized polyester copolymerized with a reactive flame retardant, a known method may be used, and a method of polycondensation by mixing a dicarboxylic acid, a derivative thereof, a diol component, a derivative thereof and a reactive flame retardant, or a thermoplastic polyester by ethylene glycol, etc. The method of depolymerizing using the diol component of this, mixing a reaction flame retardant at the time of depolymerization, and polycondensing again, and obtaining a copolymer etc. are preferable.

The polymer (B) used in the present invention is at least one polymer selected from the group consisting of polyarylate (Bl), polycarbonate (B2), and polyamide (B3), and two or more kinds thereof may be mixed and used. Also good.

The polyarylate (B1) means a wholly aromatic polyester composed of an aromatic dicarboxylic acid component and an aromatic diol component, and may be produced by any of the interfacial polymerization method, the solution polymerization method and the melt polymerization method. As for the said polyarylate (Bl) component, 1 type, or 2 or more types of mixtures chosen from isophthalic acid, its derivative (s), and / or terephthalic acid, its derivative (s), and the polyarylate which consists of an aromatic diol component are preferable, Specifically, Examples of the aromatic dicarboxylic acid component of the B1 component include polyhydric carboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, and derivatives thereof. Moreover, as an aromatic diol component of the said B1 component, dihydric phenols, resorcinol, hydroquinone, biphenol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy) And hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxyphenyl) propane and the like. Among these, in consideration of the availability and the like, a polyarylate consisting of a mixture of terephthalic acid and isophthalic acid and 2,2-bis (4-hydroxyphenyl) propane is more preferable.                     

As said polycarbonate (B2), aromatic polycarbonate, aliphatic polycarbonate, aliphatic-aromatic polycarbonate, etc. are mentioned. Generally, 2, 2-bis (4-oxyphenyl) alkanes, bis (4-oxyphenyl) ethers, bis (4-oxyphenyl) sulfones, bis (4-oxyphenyl) sulfides or bis (4- Polymers or copolymers composed of bisphenols such as oxyphenyl) sulfoxides, and the like, and polymers using bisphenols substituted with halogens according to the purpose, and the like, and the like. -Bis (4-oxyphenyl) alkanes are suitably used.

Examples of the polyamide (B3) include homopolymers of nylon 6, nylon 66, nylon 46, nylon 69, nylon 610, nylon 612, nylon 11, nylon 12, and polymethyleneadipamide (nylon MXD6) or copolymers thereof. Or a mixture thereof, and the like, of which a homopolymer of nylon 66 is suitably used in view of heat resistance and the like.

Moreover, in this invention, it is preferable to contain 10-30 weight% of polyarylates in a polymer whole component, and it is more preferable to contain 15-20 weight%. When the polyarylate is less than 10% by weight, it tends to melt and drip easily when burned, and when it is more than 30% by weight, heat resistance tends to be lowered.

In the present invention, in order to satisfy the flame retardancy required as the fiber for artificial hair, in the case of using or not using a thermoplastic copolymerized polyalkylene terephthalate copolymerized with the above-mentioned reactive phosphorus flame retardant as the polymer (A) It is preferable to add a flame retardant (C) to the said polymer component.

The flame retardant (C) used in the present invention is not particularly limited, but a phosphorus flame retardant which is generally used generally can be used, and specifically, a phosphate compound, a phosphonate compound, a phosphinate compound, and a phosphine And organic phosphorus compounds such as oxide compounds, phosphonite compounds, phosphinite compounds, phosphine compounds and condensed phosphate ester compounds. Moreover, it is preferable that it is at least 1 sort (s) chosen from the group which consists of these as a flame retardant (C), and it is more preferable that it is at least 1 sort (s) chosen from the group which consists of the said condensed phosphate ester type compound.

As the flame retardant (C), halogenated compounds represented by halogenated cycloalkane compounds, aromatic and aromatic ether halogen compounds, bisphenol A skeleton halogenated compounds, imide halogenated compounds, halogenated polystyrenes, and the like, in addition to the organophosphorus compounds, You may use together the said halogen type compound and antimony compound, and other well-known flame retardants.

In addition, even when the thermoplastic copolymer polyalkylene terephthalate copolymerized with the reactive phosphorus flame retardant is used as the polymer (A), it is possible to add a flame retardant within a range that does not impair the physical properties of the polyester fiber.

The amount of the flame retardant (C) added is 100 parts by weight in total of polymer components such as the polymer (A) and the polymer (B) when the thermoplastic copolymer polyalkylene terephthalate copolymerized with the reactive phosphorous flame retardant is used as the polymer (A). It is preferable to add 1-20 weight part with respect to it, More preferably, it is 5-10 weight part. If the added amount of the flame retardant (C) is less than 1 part by weight, it is difficult to obtain a flame retardant effect, and if more than 20 parts by weight, mechanical properties are impaired. In addition, when using a phosphorus flame retardant as a flame retardant (C), it is preferable to add 0.05-15 weight part in conversion of phosphorus atomic weight with respect to 100 weight part of polymer components total, and it is more preferable to add 0.1-12 weight part Do. If the added amount of the phosphorus flame retardant is less than 0.05 part by weight, it is difficult to obtain a flame retardant effect, and when more than 15 parts by weight, mechanical properties are impaired.

Since polyester fiber is a flammable material, flame retardancy is inadequate, and in ordinary polyester fiber which is not especially flame retardant, it ignites and burns easily by the approach of a flame, and burns well. Moreover, it is very dangerous with drips, ie, melt dripping of resin, especially in the state which attached the product to a head part. Therefore, in the polyester fiber of this invention, it disperse | distributes suitably by disperse | distributing a polymer (B) to a polymer (A), and using a flame retardant, and also avoids problems, such as drip property.

In the present invention, when a mixture of the polymer (A) and the polymer (B) is used as the polymer component, the phase structure of the resin composition constituting the polyester fiber has a sea island structure, and the polymer (A) Of the polyester phase is sea, and the polymer (B) is island. In the polyester fiber for artificial hair of the present invention, in order to enable curl setting at 80 ° C to 200 ° C, the two components of the polymer (A) and the polymer (B) are transesterified or ester-amide exchanged. In order not to react, it is necessary to melt-knead so that fibrous physical properties can be maintained. That is, it is necessary to prevent the original heat resistance, melt viscosity, and strength fall of polyester by transesterification or transesterification reaction.                     

When the two components of the polymer (A) and the polymer (B) are melt kneaded, a transesterification reaction or an ester-amide exchange reaction can usually be caused. In particular, the transesterification reaction can usually occur only by melt kneading the two components, but in order to suppress it, even if the kneading time is shortened, a uniform and fine dispersion cannot be achieved, or when a sufficient kneading time is taken, it causes an exchange reaction. By uniformly mixing with each other, the island-in-the-sea structure in which the polymer (B) is dispersed is not formed. In order to promote the dispersion of the polymer (B) and to suppress the exchange reaction, it is preferable to use an antioxidant (D) in the present invention as the compound having the ability to inhibit the transesterification reaction, and as the component (D), a phosphite compound It is more preferable to use.

Examples of the phosphite-based compound include trialkyl phosphites such as trioctyl phosphite and tridecanyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, and tris (2,4-di (t-butyl)). Phosphite compounds such as triaryl phosphites such as phenyl) phosphite and alkylaryl phosphites such as didecanylphenyl phosphite, decanyl diphenyl phosphite and octyl diphenyl phosphite.

It is preferable to add 0.05-5 weight part with respect to a total of 100 weight part of a polymer component, and, as for the addition amount of antioxidant (D), it is more preferable to add 0.1-3 weight part. When the amount of the antioxidant (D) added is less than 0.05 part by weight, a transesterification reaction or an ester-amide exchange reaction occurs, so that a decrease in mechanical properties or a gloss removal effect cannot be obtained. When the addition amount exceeds 5 parts by weight, the heat resistance and the mechanical properties of the fiber decrease, or the breakage of the yarn occurs during the melt spinning process due to the decrease in the melt viscosity, thereby making the process unstable.

In this invention, when using the mixture of a polymer (A) and a polymer (B) as a polymer component, it is preferable that the weight ratio is the range of polymer (A) / polymer (B) = 90/10-70/30, More preferably, it is the range of 88/12-75/25. If the polymer (A) is larger than the above range, irregularities on the surface of the fiber become smaller and smaller, so that the gloss removal effect cannot be obtained. On the other hand, when the polymer (B) is larger than the above range, a transesterification reaction or an ester-amide exchange reaction occurs, so that a lowering of mechanical properties or a gloss removal effect can be obtained, or the melt viscosity becomes too high and melt spinning becomes difficult. Moreover, as a polymer component, you may use another polymer other than a polymer (A) and a polymer (B) together.

The short fiber fineness of the polyester fiber of this invention is 30-70 dtex, Preferably it is 40-60 dtex. If the short fiber fineness is less than 30 dtex, the touch tends to be too soft and the curl holding force tends to be weak. If the short fiber fineness exceeds 70 dtex, the touch tends to be too hard and the curl holding force tends to be too strong.

The manufacturing method of the resin composition which comprises the polyester fiber of this invention is not restrict | limited, For example, in polymer components, such as a polymer (A) and a polymer (B), (C) component, ( After dry compounding D) component, the method of melt-kneading using various general kneading machines is mentioned. As an example of a kneader, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, a kneader, etc. are mentioned, A twin screw extruder is preferable.

The polyester fiber of this invention can be manufactured by a normal melt spinning method. That is, first, the resin composition is melt-spun with the temperature of an extruder, a gear pump, a nozzle, etc. at 270-310 degreeC, a discharge sand tank is passed through a spinning cylinder, and it cools to below glass transition point. Undrawn yarn is obtained by pulling at a speed of 50 to 5000 m / min. It is also possible to cool the discharge yarn in a water tank containing water for cooling and to control fineness. The temperature and length of a spinning cylinder, the temperature and blowing amount of a cooling wind, the temperature of a cooling tank, a cooling time, and a take-up speed can be adjusted suitably according to discharge amount and the number of holes of a nozzle.

The obtained non-drawn yarn is thermally drawn, but the stretching may be carried out by any of two methods of winding the undrawn yarn and stretching it, and a direct radial stretching method which draws continuously without sensing. Hot stretching is performed by the single-stage stretching method or the two or more stages of multistage stretching method. As a heating means in hot drawing, a heating roller, a heat plate, a steam jet apparatus, a hot water tank, etc. can be used, These can be used together suitably.

Subsequent to the thermal stretching, heat treatment is performed. Here, before heat processing, you may provide a spinning emulsion as needed, and you may provide a spinning emulsion after heat processing. Arbitrary heating means can be used for heat processing similarly to the case of the said thermal drawing. By treating the stretched yarn obtained in the above-mentioned thermal stretching process by tension or relaxation, and using them in combination, the residual shrinkage stress of the stretched yarn is eliminated to stabilize the shape, and when the artificial hair product after completion is actually curled, the gradation Can be prevented.

As heat processing temperature, it is preferable to carry out at 160 degreeC-220 degreeC, More preferably, it is 180 degreeC-200 degreeC. When the heat treatment temperature is lower than 160 ° C., the removal of residual shrinkage stress after stretching is insufficient and the shape cannot be stabilized. Therefore, when the curled hair is finished at a temperature exceeding 160 ° C., especially at 180 ° C. or higher, Shrinkage or gradation may occur, and at the temperature exceeding 220 degreeC, a fiber may soften and a process may become unstable and the appearance of a fiber may be impaired. In this invention, it is necessary to make thermal contraction rate in 200 degreeC into 5% or less, and this heat processing is important.

Although the processing conditions of the polyester fiber of this invention are not specifically limited, Although it can process similarly to normal polyester fiber, the pigment, dye, and a preparation used etc. which are good in weather resistance and flame retardance are used. It is desirable to.

Moreover, the polyester fiber of this invention can contain various additives, such as a flame retardant, a heat resistant agent, a light stabilizer, a fluorescent agent, antioxidant, an antistatic agent, a pigment, a plasticizer, a lubricating agent, as needed.

The polyester fiber of this invention is excellent in the curl setting property using a beauty heating apparatus (hair iron etc.), and is excellent also in the retention of curl. In addition, an oil agent such as a fiber surface treatment agent and a softening agent can be used to impart touch and texture to bring the texture closer to human hair.

In addition, when using the polyester fiber of this invention as artificial hair, you may use together with other artificial hair materials, such as modacryl, polyvinyl chloride, and nylon other than human hair.

<Example>

Next, although an Example demonstrates this invention concretely, this invention is not limited to these.                     

In addition, the measuring method of a characteristic value is as follows.

(Strength and elongation)

Tensile elongation of filament was measured using the INTESCO Model 201 type made by Intesco. One filament of 40 mm in length is taken, and 10 mm of both ends of the filament are sandwiched between sheets of paper (sticking paper) to which double-sided tape with adhesive is attached, followed by air drying overnight to prepare a sample having a length of 20 mm. The sample was attached to the tester, the test was performed at the temperature of 24 degreeC, humidity 80% or less, the load 1 / 30gf x fineness (denier), and the tension rate 20mm / min, and the elongation was measured. The test was repeated 10 times under the same conditions, and the average value was taken as the elongation of the filament.

(Heat shrinkage)

The thermal contraction rate of a filament was measured using the SSC5200H thermal analysis TMA / SS150C by Seiko Denso Kogyo Co., Ltd. Ten filaments of 10 mm in length were taken, and a load of 5.55 mg / dtex was applied, measured at a range of 30 to 280 ° C. at a heating rate of 3 ° C./min, and thermal shrinkage at 200 ° C. was obtained from the results.

(Limit oxygen index)

16 cm / 0.25 g of filament is weighed, and the end is lightly attached to a double-sided tape and braided with a string machine. When twisted sufficiently, the center of the sample is folded in half and the two are braided together. Tape the end to the cell with tape and make it 7 cm long. Predrying is carried out at 105 DEG C for 60 minutes, and further dried for 30 minutes or more with a desiccator. The dried sample is adjusted to a predetermined oxygen concentration and ignited from the top by an igniter tightened to 8-12 mm after 40 seconds, and the igniter is isolated after ignition. Burn at least 5cm or continue the carbon concentration for more than 3 minutes, repeat the test 3 times under the same conditions and set the limit oxygen index.

(Melting point)

Melting | fusing point was measured using the Seikoden Kogyo Co., Ltd. product DSC220C. Samples of the filaments were finely cut with a cutter or scissors, and 10 mg were precisely weighed and placed in an aluminum pan to set in the apparatus. The measurement temperature range was -20 ° C to 340 ° C (actually, the measurement range was approximately -10 ° C to 290 ° C), the temperature increase rate was 20 ° C / min, and the nitrogen flow rate at the time of measurement was 30 ml / min. The main (maximum) melting peak top was calculated | required from the obtained chart, and this was made into melting | fusing point.

(Melt viscosity)

It carried out using the capillograph by the Toyo Seki Seisakusho Co., Ltd. The test speed was measured as 50 mm / min, orifice radius 0.0500 cm, barrel radius 0.4775 cm, barrel temperature 280 degreeC, and melt viscosity was computed by the following formula.

Shear pressure τ = Pr / 2L = Fr / 2πR ² L (1)

Shear rate γ = 4Q / πr ³ = 4V / 60πr ³ (2)

Apparent viscosity η = τ / γ (3)

(P is the barrel internal pressure, F is the extrusion load, R is the barrel radius, r is the capillary radius, L is the capillary length, Q is the flow value, V is the extrusion amount, and v is the extrusion speed.)                     

(Drip)

Tie 100 filaments of about 50 dtex of fineness, one end is sandwiched between the clamps, fixed to the stand, and hanged vertically. A flame of 20 mm was brought close to the filament fixed, and a length of 100 mm was burned, and the number of drips at that time was counted, and if the number of drips was 5 or less,?

(Cold setting)

The filament of 160 mm / 0.1 g is extended straight, and both ends are taped and heated at 100 degreeC for 40 minutes. After cooling to room temperature, cut into 85 mm, fold in half, connect the both ends with sewing thread, hang on a rod of φ4 mm, attach a spindle to load 6.7 mg / dtex, and apply it for 24 hours at 30 ° C and 60% RH. Keep it. Remove the weight, leave for 5 minutes, cut into 80mm, and measure the bending state (angle) of the filament. It is most preferable to make this an index of the setting property at low temperature, and to immediately return to (180 ° C).

(Curl retention)

The filament in the form of a hair was wound on a pipe of φ32 mm, curled at 100 ° C. for 60 minutes, aged at room temperature for 60 minutes, and then one end of the curled filament was fixed and suspended. Examine the change over time of the filament length. It is preferable that this is an index of the ease of curling and the retention, and the shorter the initial length is, the curl setting at lower temperature is possible and the higher temperature can be set.                     

In addition, the curl elongation after leaving for 7 days is computed and expressed as a percentage by the above-mentioned curl holding force evaluation by (filament length after 7 days leaving-initial filament length) / initial filament length x100. It is an indicator of the retention of the filament relative to its initial length.

(Iron setting)

It is an index of the ease of curl setting by a hair iron and the retention of curl shape. The filament is lightly sandwiched between the hair irons heated to 180 ° C., and pulled three times to preheat. The fusing between the filaments, the combing, the filament shrinkage, and the breakage of the filaments at this time are visually evaluated. Next, the preheated filament is wound on a hair iron, held for 10 seconds, and the iron is taken out. The ease of pulling out at this time (load out property) and the retention of curl at the time of pulling out were visually evaluated.

Examples 1-10

To 100 parts by weight of a mixture of polyester, polyarylate or polycarbonate or polyamide dried at a water content of 100 ppm or less, a condensed phosphate ester compound and a phosphite compound as a phosphorus flame retardant are mixed at a ratio shown in Table 1 and colored. 1.5 parts by weight of polyester pellet PESM6100 BLACK (manufactured by Daiichi Seika Kogyo Co., Ltd., carbon black content 30%) was added to dry paste, fed to an extruder, melt kneaded at 300 DEG C, and pelletized to be 100 ppm or less in moisture. Dried over. Subsequently, the molten polymer is discharged using a spinning nozzle having a nozzle hole having a rounded nozzle hole with a cross section of 0.5 mm in diameter, and cooled in a water bath at a water temperature of 50 ° C. provided at a position of 30 mm below the nozzle. It wound up at speed and got undrawn. The resultant unstretched yarn was stretched in a hot water bath at 80 ° C. to be 4 times drawn yarn, and was wound and heat-treated at a speed of 100 m / min using a heat roll heated at 200 ° C. to give a polyester fiber having a single fiber fineness of about 50 dtex. (Multifilament) was obtained.

Example 11

To 100 parts by weight of a mixture of a reactive phosphorous flame retardant copolymer polyester (flame retardant PET, SBT-3 manufactured by HUVIS) and polyarylate dried at a moisture content of 100 ppm or less, the phosphite compound was mixed at a ratio shown in Table 1, and colored. Polyester pellet PESM6100 BLACK (manufactured by Daiichi Seika Kogyo Co., Ltd., carbon black content 30%) was added to dry mix, fed to an extruder, melt kneaded at 300 ° C, pelletized, and then moisture content of 100 ppm or less. Subsequently, the molten polymer was discharged using a spinning nozzle having a nozzle hole having a rounded nozzle hole with a cross section of 0.5 mm in diameter, cooled in a water bath of 50 ° C at a water temperature installed at a position of 30 mm below the nozzle, It wound up at the speed | rate and obtained undrawn yarn The obtained undrawn yarn was extended | stretched in the hot water bath of 80 degreeC, and made into 4 times stretched yarn, using the heat roll heated at 200 degreeC. It wound up at 100 m / min and heat-processed, and obtained the polyester fiber (multifilament) whose short fiber fineness is 50 dtex around.

Example 12

With respect to 100 parts by weight of the mixture of polyester and polyarylate dried at a water content of 100 ppm or less, brominated polystyrene and phosphite compounds were mixed at a ratio shown in Table 1 as the bromine-based flame retardant. A polyester fiber (multifilament) having a fiber fineness of 50 dtex was obtained.

For the fibers obtained in Examples 1 to 12, the melt viscosity, the fineness, the strength, the elongation, the heat shrinkage, the melting point, the flame retardancy evaluation, the limit oxygen index, the drip property evaluation results, and the evaluation of artificial hair. Table 1 shows the results of evaluating the cold setting property, curl holding power, and iron setting property. In Examples 1 to 12, it was possible to obtain a polyester-based artificial hair fiber having excellent setting ease, setting retention, heat resistance, drip resistance, and flame retardancy.

TABLE 1

Comparative Example 1

Polyethylene terephthalate and polyarylate dried at a water content of 100 ppm or less are mixed at a ratio shown in Table 2, and a condensed phosphate ester compound and a phosphite compound are mixed at a ratio shown in Table 2 with respect to 100 parts by weight of the mixture, Color polyester pellet PESM6100 BLACK (manufactured by Daiichi Seika Kogyo Co., Ltd., carbon black content: 30%) was added to dry blending, fed to an extruder, melt mixed at 300 ° C, pelletized, and then 100 ppm of moisture. Next, molten polymer was discharged using a spinning nozzle having a nozzle hole with a round cross section of a nozzle diameter of 0.5 mm, cooled in a bath at a water temperature of 50 ° C. installed at a position of 30 mm below the nozzle, and 100 m / min. The unstretched yarn was wound up at a speed of to obtain an undrawn yarn, which was stretched in a hot water bath at 80 ° C. to be 4 times drawn yarn, and 200 ° C. Heat treatment was performed using a heated heat roll at a speed of 100 m / min to obtain a polyester fiber (multifilament) having a short fiber fineness of 52 dtex, but the limit oxygen index as a flame retardancy evaluation, shrinkage at 200 ° C., and drip A satisfactory fiber could not be obtained.

Comparative Example 2

A polyester fiber having a single fiber fineness of 50 dtex in the same manner as in Comparative Example 1 except that polyethylene terephthalate, polybutylene terephthalate, and polyarylate dried at a moisture content of 100 ppm or less were mixed at a ratio shown in Table 2. Filament). However, satisfactory fibers were not obtained, such as slightly poor curl holding power as well as easy evaluation of artificial hair, drip and fusion of fibers even when iron setting, and poor load-out property.

Comparative Example 3

A polyester fiber (multifilament) was obtained in the same manner as in Comparative Example 1 except that 65 parts by weight of polyethylene terephthalate and 35 parts by weight of polyarylate were used. Could not.

Comparative Example 4

A polyester-based fiber (multifilament) having a short fiber fineness of 48 dtex was obtained in the same manner as in Comparative Example 1 except that 80 parts by weight of polyethylene terephthalate and 20 parts by weight of polyarylate were not added. However, satisfactory fibers could not be obtained in the marginal oxygen index and the dripability as flame retardancy evaluation.

Comparative Example 5

A polyester fiber having a single fiber fineness of 51 dtex was obtained in the same manner as in Comparative Example 1 except that 80 parts by weight of polyethylene terephthalate and 20 parts by weight of polyarylate were added, and 30 parts of a phosphorus flame retardant was added. Although the marginal oxygen index showed a high value, satisfactory fiber was not obtained, such as a considerable drip during combustion, and iron gradation and fusion of the fiber in the iron setting property.

Comparative Example 6

85 weight part of polyethylene terephthalates and 15 weight part of polyarylates were carried out similarly to the comparative example 1 except not adding a phosphite type compound, and the polyester fiber (multifilament) of 50 dtex of single fiber fineness was obtained. However, a satisfactory fiber was not obtained, such as a significant decrease in melting point, significant drip during combustion, fiber gradation and fusion even in iron setting, and poor load-out properties.

With respect to the fibers obtained in Comparative Examples 1 to 6, the cold setting property, curl holding force, and iron setting property were evaluated as evaluation results of elongation and heat shrinkage rate, flame retardancy evaluation, evaluation results of limit oxygen index, dripability, and evaluation of artificial hair. One result is shown in Table 2. In Comparative Examples 1-6, the target polyester fiber for artificial hair could not be obtained at all.

TABLE 2

According to the present invention, in addition to maintaining fiber properties such as heat resistance and elongation, which are the features of polyester fibers, the present invention satisfies the required performance as artificial hair such as ease of setting and setting retention, and is also a conventional polyester fiber for artificial hair. Drip resistance and flame retardancy that were not available can be obtained.

Claims (14)

A fiber for polyester artificial hair having at least 180 ° C of iron setting, having heat resistance at a thermal shrinkage of 200 ° C of 5% or less, and flame retardancy having a limiting oxygen index LOI of 25 or more. The method of claim 1, Curl | Karl setting in the temperature range of 80 to 200 degreeC is possible, The fiber for polyester artificial hairs whose curl elongation rate when the curled fiber is left still at 25 degreeC for 7 days or less is 35% or less. The method of claim 1, The fiber for polyester artificial hairs whose melt viscosity of the resin composition which comprises a fiber is 50-300 Pa.sec at a shear rate of 600 sec ^-1 and a temperature of 280 degreeC. delete The method of claim 1, A polyester-based artificial hair fiber having a polyalkylene terephthalate of 70% by weight or more in the polymer component in the resin composition constituting the fiber. The method of claim 5, wherein The fiber for polyester artificial hairs whose said polyalkylene terephthalate is at least 1 sort (s) chosen from the group which consists of a polyethylene terephthalate, a polypropylene terephthalate, and a polybutylene terephthalate. The method of claim 5, wherein The polyester-based artificial hair fiber, wherein the polyalkylene terephthalate is a thermoplastic copolymerized polyalkylene terephthalate copolymerized with a reactive phosphorous flame retardant. The method of claim 5, wherein A polyester-based artificial hair fiber containing at least one member selected from the group consisting of polyarylate, polyamide, and polycarbonate as another polymer component in the resin composition constituting the fiber. The method of claim 8, A polyester-based artificial hair fiber containing 10 to 30% by weight of polyarylate as another polymer component in the resin composition constituting the fiber. The method of claim 1, The fiber for polyester artificial hairs which the resin composition which comprises a fiber contains 1-20 weight part of flame retardants with respect to 100 weight part of polymer components in total. The method of claim 10, A fiber for artificial artificial hair, wherein the flame retardant is phosphorus-based and contains 0.05 to 15% by weight, based on the atomic weight of phosphorus, based on the polymer component. The method of claim 1, The fiber for polyester artificial hairs which the resin composition which comprises a fiber contains 0.05-5 weight part of antioxidant with respect to 100 weight part of polymer components in total. The method of claim 12, Polyester-based artificial hair fiber, wherein the antioxidant is phosphite-based. The method of claim 1, Polyester fiber for artificial hair having a short fiber fineness of 30 to 70 dtex.