JPS63211311A - Artificial hair - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to artificial hair used in wigs, hair wigs, and the like.

<Prior Art> Conventionally, various synthetic m-fibers have been used for artificial hair such as wigs and hair rugs, but one that is fully satisfactory in terms of strength, gloss, feel, etc. has not yet been developed.

For example, in the case of polyvinyl chloride fibers, the strength is low and when the hair is styled after waving, it easily gets caught and breaks. Furthermore, the color fastness is low, and even those dyed with cationic dyes easily change color and fade due to exposure to light while wearing the wig.

Therefore, in the case of black artificial hair, it is obtained by mixing a black pigment with a fiber raw material and spinning it into yarn, but even in this case, the blackness of natural hair cannot be obtained because of the large amount of surface reflected light. In addition, heat set durability is low, so bathing, showering,
Curls and waves disappear under conditions such as saunas and sunlight. Therefore, when artificial hair is partially worn, only that part of the artificial hair is deformed, so that it can be immediately recognized that the hair is artificial. Also, static electricity is generated due to the friction during hair styling, which causes bristling and dust. In other words, the current artificial hair has low strength and silk factor, cannot achieve a black hue close to that of natural hair (particularly black with a reddish or bluish tinge), and also has poor heat-setting durability. It has a loose texture and cannot be used as a substitute for basolateral natural hair.

Means for Solving Problems> As a result of intensive research to solve these problems, the inventors of the present invention have found that polyester monofilament fibers containing a micropore-forming agent are dyed by making the fiber surface microporous by, for example, alkali treatment. Or, by adding a thin film of antistatic agent to the surface of the dyed yarn, artificial hair that simultaneously satisfies high color development, heat setting durability, high strength, mild luster, soft touch properties, and rough antistatic properties. We have arrived at the present invention by discovering that the following can be obtained.

<Structure of the Invention> That is, the present invention provides: r(1) Artificial hair made of synthetic fibers, characterized in that the fibers are polyester monofilaments having micropores at least on the fiber surface.

(2) In artificial hair made of synthetic fibers, the fibers are polyester monofilaments that have at least micropores on the fiber surface and have an antistatic agent with an electrical resistance value of 1010 Ω/cm or more attached to the fiber surface. Features and artificial hair. ”.

The polyester fiber used in the present invention must contain a micropore-forming agent, and the effects of the present invention cannot be obtained with polyester fibers that do not contain a micropore-forming agent.

Such a micropore-forming agent can be used to form micropores on the surface or inside the polyester fiber by alkaline molar reduction treatment, etc., and after dyeing, it can produce a natural hair-like texture, hygroscopicity, water absorption, depth of two colors, salmon brightness, etc. Although there is no need to specifically limit the material as long as it can substantially perform its functions, the effects of the present invention are particularly effective when the micropore-forming agent is a compound containing a metal.

Among the above-mentioned micropore-forming agents, those that are particularly desirable in order to achieve the object of the present invention include (a) 0.3 to 3 mol % of a phosphorus compound represented by the following general formula (I> (0)m RIO-P-OX... (I) R2 and (b) an alkaline earth metal compound were added to (a) and (b). ) without reacting in advance, and added so that the total number of equivalents of metals (a) and (b) is 2.0 to 3.2 times the number of moles of the phosphorus compound of (a). As a result, insoluble fine particles precipitate inside the polyester reaction system.

In the above formula (1) representing a phosphorus compound, 1 (1 and R2 are a hydrogen atom or a monovalent organic group. This monovalent organic group is an alkyl group, an aryl group, an aralkyl group, or a +(
CH2) kR3+ (However, R3 is a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.

l is an integer of 2 or more, R is an integer of 1 or more), etc.
' and R2 may be the same or different. X is a hydrogen atom, a monovalent organic group, or a metal, and the monovalent organic group is the same as the definition of the organic group in R' and R2 above, and R
+ and R2 may be the same or different, and the metals are particularly preferably alkali metals and alkaline earth metals, among which Li, Na, K, Hg1/2, Cal/
2 is particularly preferred. m is an integer of O or 1;

Such phosphorus compounds include, for example, phosphoric acid, trimedel phosphate, phosphoric triester such as triethyl phosphate,
Phosphoric acid mono- and diesters such as medyl acid phosphate, edyl acid phosphate, sulfur triesters such as sulfuric acid, trimethyl phosphite, triethyl phosphite, methyl acid phosphite, ethyl acid phosphite. Phosphorous acid mono- and diesters such as phite, phosphorus compounds obtained by reacting the above-mentioned phosphorus compounds with glycol and/or water, and further the above-mentioned phosphorus compounds in predetermined amounts of alkali metal compounds such as Li, Na, K, etc. Or) one or more phosphorus compounds selected from phosphorus compounds obtained by reacting with compounds of alkaline earth metals such as Ig, Ca, etc. can be used.

The alkaline earth metal compound to be used in combination with the phosphorus compound is not particularly limited as long as it reacts with the phosphorus compound to form a salt insoluble in polyester, and alkaline earth metal acetates and oxalates can be used.

Organic carboxylates such as benzoates, borates, inorganic acid salts such as sulfates, halides such as chlorides, chelate compounds such as ethylenediaminetetraacetic acid complexes, hydroxides,
Oxides, methylates, alcoholades such as thilates,
Examples include phenolates. In particular, organic carboxylic acid salts, halides, chelate compounds, and alcoholades which are soluble in ethylene glycol are preferred, and organic carboxylic acid salts are particularly preferred. The above alkaline earth metal compounds may be used alone or in combination of two or more.

In addition to the above-mentioned micropore forming agents, silica sol, dry process silica containing aluminum oxide, dry process silica with blocked silanol groups on the particle surface, alumina sol, fine particulate alumina, ultrafine particulate titanium oxide, and fine particulate form. Inert inorganic fine particles made of at least one type selected from calcium carbonate and having an average primary particle diameter of 100 mμ or less are preferable. The content of such inert inorganic fine particles in the polyester fiber is 0.0% relative to the polyester fiber.
A range of 1 to 10% by weight is preferred, and a range of 0.3 to 5% by weight is particularly preferred.

It is desirable to add the inert fine particles as a dispersed slurry or sol of glycol, alcohol, water, etc. at any stage until the polyester synthesis reaction is completed.

The polyester containing the micropore-forming agent thus obtained is made into i-fiber by a normal spinning method.

The polyester used in the present invention is a polyester containing terephthalic acid as the main acid component and alkylene glycol as the main glycol component.

It may also be a polyester in which a part of the terephthalic brewing component is replaced with another difunctional carboxylic acid component, and/'
Alternatively, it may be a polyester in which a part of the glycol component is replaced with a glycol other than the main component.

Such polyesters may be synthesized by any method. For example, in the case of polyethylene terephthalate, it is usually a direct esterification reaction between terephthalic acid and ethylene glycol, a transesterification reaction between a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, or a transesterification reaction between terephthalic acid and ethylene oxide. The first stage reaction involves reacting to produce a glycol ester of terephthalic acid and/or its low polymer, and the first stage reaction product is heated under reduced pressure to undergo a polycondensation reaction until a desired degree of polymerization is achieved. It is produced by a second stage reaction.

When melt-spinning the micropore-forming agent-containing polyester, any conventional melt-spinning method for polyester fibers can be used.

Stretching may be carried out if necessary, and in that case, for example, the film may be heated and stretched using a hot roller or a hot pin, and if necessary, heat set using a plate heater. In that case, it is preferable to select a draw ratio as low as to increase the residual bacteria elongation of the drawn yarn to 30 to 50%.

The cross-sectional shape of the polyester fibers may be round or irregular. A round cross section is suitable for enhancing color development, and a polygonal cross section is suitable for adding a natural-looking gloss. The single yarn fineness is preferably 20 to 80 deniers. In particular, it is better to use a mixture of 3 to 5 types of single yarns with m degree, which are not close to artificial hair (for pulling).Those with low single yarn fineness give a stiff drape.

In addition, high single yarn fineness provides hair styling properties when combed, tension, and heat setting durability. It may also be mixed with other fibers or randomly mixed with turbulent air.

The polyester monofilament fiber used in the present invention may contain optional additives, such as Catalyst 1 color inhibitor, heat resistant agent, optical brightener, and brightening agent, if necessary.

A coloring agent or the like may be included.

The thus obtained polyester monofilament fiber is subjected to alkali weight reduction treatment using an alkali compound to form micropores arranged in the fiber axis direction.

The alkaline compounds used here include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and sodium carbonate.

Examples include potassium carbonate. Among these, sodium hydroxide and potassium hydroxide are particularly preferred.

Also cetyltrimethylammonium bromide.

Alkali weight loss accelerators such as lauryldimethylbenzyl ammonium chloride and the like can be used as appropriate.

The alkali weight loss treatment may be carried out by a high-pressure method such as a dyeing machine or by a normal-pressure liquid submersion method, but it can also be carried out by a pad steam method or a cold batch method. The amount to be weighed by this alkali weight loss treatment is preferably 2% by weight or more based on a single fiber, and usually can be carried out in the range of 2 to 40% by weight. If necessary, a scouring step may be added for the purpose of removing oil and the like before the alkali weight reduction treatment.

As another technical means for making the fiber surface rough, a low temperature plasma irradiation method can also be used. Regarding the size of the micropores obtained by the alkali weight loss treatment, "1", where the value having the maximum frequency in the frequency distribution of the micropores is along the direction orthogonal to the fiber axis, is in the range of 0.1 to 0.5 μm. Further, the length in the direction of the fiber axis is preferably in the range of 0.5 to 5 μm, and the depth of the hole toward the fiber axis is preferably in the range of 0.1 to 0.3 μm. When the diameter of the micropores becomes large, the color tone becomes pastel due to the influence of light scattering. Therefore, in order to obtain deep and clear color development, it is preferable to keep the size of the micropores within the above range.

To change the shape of micropores, consider the intrinsic viscosity of polyester, the amount of micropore-forming agent, spinning speed, and stretching ratio.

The test is carried out by variously changing the conditions such as the alkali reduction rate.

The monofilament thus treated is then dyed. The dye to be used is preferably a disperse dye or the like, and is preferably of a high fastness type. In general, disperse dyes (soft types with a molecular weight of less than 150 and hard types with a molecular weight of 150 or more are known), and the soft types with good level dyeing properties are mainly used.However, in the present invention, It is preferable to use hard-type disperse dyes for puru dyeing, and it is particularly preferable to use ones with a molecular weight of about 250 to 350.However, although the hard-type dyes have good fastness, they are uniform. Dyeing auxiliary agents are used as the dyeability is somewhat difficult.Additionally, alkaline reduction treatment may be applied after dyeing.In other words, the fiber 1
A polyester monofilament prepared by mixing H with a colored pigment or a polyester monofilament dyed with a disperse dye may be subjected to an alkali weight reduction treatment.

Furthermore, the polyester monofilament of the present invention imparts a durable antistatic agent to the finely textured fiber surface after dyeing. The antistatic agent is preferably applied uniformly in a thin film form in an amount of 0.05 to 6% by weight based on the 11i material.

Examples of antistatic agents include (1) anionic antistatic agents; copolymers of polyacrylic acid, methyl methacrylate, etc., and maleic anhydride; ester derivatives of copolymers of styrene and maleic anhydride; and polyethylene glycol; polyvinyl Sulfonic acids such as sulfonic acid, ethyl hydrogen-4-amino-6-anilo-S-triazinylmethyl small sulfonic acid (2) Cationic antistatic agent Acrylic acid such as the quaternary ammonium salt of diethylamine ethyl methacrylate]-ster derivatives, acrylic acid acid derivatives such as acrylamide methylene urea, vinyl ether derivatives such as polyvinyl-2-chloroethyl ether pyridinium salt, quaternary ammonium salts from copolymers of 2-vinylpyridine and styrene, polyethylene glycol polyamines (3) Cadionic antistatic agent 1.3.5-Triacryloyl-hexahydro-S-triazine, etc. (4) Nonionic antistatic agent Ester of methacrylic acid and polyethylene glycol,
A reaction product of polyethylene glycol and O-rohydrin, an N-methoxymethylated polyamide.As an antistatic agent, a polyester polyether consisting of terephthalic acid and/or isophthalic acid or their lower alkyl esters, lower alkylene glycols, and polyalkylene glycols is used. These include aqueous dispersions of block copolymers.

The molar ratio of each component of these block copolymers is lower alkylene glycol: polyalkylene glycol = 1:2
A frequency of ~3:1 is preferable from the viewpoint of antistatic properties. As a treatment method, a pad curing method, an in-bath dilution method, a pad steaming method, etc. can be used, but an in-bath adsorption method is particularly preferred. This in-bath adsorption method may be carried out as a separate treatment after dyeing, but it can also be carried out simultaneously with dyeing. In any case, after the antistatic agent is applied to the surface of the micropores, drying is performed, and if necessary, dry heat treatment is performed. Electrical resistance value is 1010Ω/
Cm or less, even when hair is styled with a synthetic resin comb, no static electricity is generated and no dust is attracted.

<Effects of the Invention> According to the present invention, by making the hair porous and dyeing it or further applying antistatic treatment, it is possible to obtain artificial hair having the following effects.

(1) Bathochromic properties and sharpness are increased due to a decrease in reflected light from the surface.

(2) Excellent heat set durability.

(3) It exhibits a mild luster similar to that of natural hair.

(4) The micro-irregularities on the surface provide a soft touch, making it easier to handle the hair with a comb, etc., and no cutting phenomenon is observed.

(5) Durable electrostatic properties are provided and static electricity is not generated during hair styling.

<Example> Examples of the artificial hair of the present invention are shown below. Incidentally, the measured values were determined by the following measuring method.

Precisely 2 on electrical resistance insulating polyethylene terephthalate film
．． Ag dotite (conductive resin paint, manufactured by Fujiji Kogyo) is applied to the cross section of a white conductive fiber with both ends cut in the cross-sectional direction to 0 cm.
I want to measure the electrical resistance value by applying a DC voltage of IKV at 20°C x 30% R11.The unit is Ω/Cff1.
).

The monofilament obtained with antistatic properties was knitted into a tube and tested using a rotary static tester at a load of 600 g and a rotation speed of 70 rpm.
, Friction cloth: I want to measure the frictional charging voltage under the conditions of cotton cloth 2
0°C x 40% R [1].

The unit is volt (V), and the smaller the number, the better the electrical conductivity, and the less dust (=-1f [(cigarette ash)).

The reflectance R (%) of the dyed fabric was measured at a wavelength of 500 IlIμ using a self-recording spectrophotometer RC-330 manufactured by Shimadzu Corporation, and the bathochromic property (K/ S) was calculated.

K/S= (1-R>2/2R Heat setting durability (hair curl setting durability evaluation plate) The emulsion multifilament was fixed at an angle of 90", heat-treated at 180℃ for 2 minutes in a hot air dryer, and then 3 in hot water at 90'C
After immersion for 0 minutes, the angle of the multifilament was measured.

(Good) ○〉Δ〉×(Poor) The gloss and tactile levels were determined based on visual sensation and touch, and compared with natural hair, the following rankings were performed.

(Mild luster similar to natural hair) ○〉Δ〉× (dazzling luster/metallic tone) (feel similar to natural hair) Q〉△〉× (hard touch like a toothbrush) Example 1 Dimethyl terephthalate 100 part, ethylene glycol 6
0 parts and 0.06 parts of calcium acetate monohydrate (0.068 mol % based on dimethyl terephthalate) were charged for transesterification, and the temperature was raised from 140°C to 230°C over 4 hours under a nitrogen gas atmosphere. The transesterification reaction was carried out while the methanol produced was distilled out of the system. Subsequently, 0.5 parts of trimethyl phosphate (0.693 mol% relative to dimethyl terephthalate) and 0.31 parts of calcium acetate monohydrate (17 parts relative to trimethyl phosphate) were added to the reaction product obtained.
2 times mole) in 8.5 parts of ethylene glycol.
Clear solution of phosphoric acid diester calcium salt 9631 purified by reaction for 60 minutes under total reflux at a temperature of 0°C.
9.88 parts of a mixed transparent solution of phosphoric acid diester calcium salt and calcium acetate obtained by dissolving 0.57 parts of calcium acetate monohydrate (0.9 times the mole relative to trimethyl phosphate) in 1 part at room temperature. was added, and then 0.04 part of antimony trioxide was added and transferred to a polymerization can. Next, the pressure was reduced from 760 mm and 11 g to 'lunHg over 1 hour, and at the same time the temperature was raised from 230'C to 285°C over 1 hour and 30 minutes. 1 mm bidirectional reduced pressure F, polymerization temperature 285°C
Then, polymerization was continued for another 3 hours, for a total of 4 hours and 30 minutes, until the intrinsic viscosity was 0.
640 and a softening point of 259°C was obtained. After the reaction was completed, the polymer was made into chips according to a conventional method.

This chip was dried by a conventional method, melt-spun at 290°C using a spinneret with 36 circular spinning holes with a hole diameter of 0.3 mm, wound at 1300 n+/mi, and then stretched to form a 40 denier fiber. 1q of monofilament drawn yarn.

The obtained yarn was treated with a 50% aqueous sodium hydroxide solution at boiling temperature according to a conventional method to obtain a monofilament fiber whose surface was made microporous with a weight loss rate of 15.2%.

This is disperse dye Dianix Black tlG
-FS (Mitsubishi Chemical Industries @Product) 15% owf, dispersion and leveling agent Disper VG (Kaisei Chemical Industry @Product) pH
After dyeing at 130°C for 60 minutes with a staining solution containing 0.3 g/l of acetic acid as a conditioner, 1 cum/2 g/l of sodium hydroxide,
80°C in an aqueous solution containing hydrosulfide 1a/l and ethylenetriaminepentaacetic acid M5 sodium salt 19/1
A black monofilament yarn with excellent color development was obtained by reduction washing for 20 minutes. In addition, the heat set durability was good and the texture was soft.

Comparative Example 1 Example 1 was carried out except that only the alkali reduction treatment step was excluded. The resulting monofilament yarn without micropores had insufficient illumination, and had a high surface reflectivity, giving it a "dazzling" feel, and the texture was crunchy and hard to the touch.

Table 1 shows Example 1. The results of Comparative Example 1 are shown.

Example 2 100 parts of dimethyl terephthalate, 6 parts of ethylene glycol
0 parts and 0.06 parts of calcium acetate monohydrate (0.066 mol % based on dimethyl terephthalate) were charged for transesterification, and the temperature was raised from 140'C to 230°C over 14 hours in a nitrogen gas atmosphere. The methanol produced was distilled out of the system before the transesterification reaction was carried out. Subsequently, 0.5 parts of trimethyl phosphate (0.693 mol% relative to dimethyl terephthalate) and 0.31 parts of calcium acetate monohydrate (1 part relative to trimethyl phosphate) were added to the reaction product obtained.
72 times mole) in 8.5 parts of ethylene glycol.
Clear solution of phosphoric acid diester calcium salt purified by reaction for 60 minutes under total reflux at a temperature of 20'C.9.
A transparent mixed solution of phosphoric acid diester calcium salt and calcium acetate obtained by dissolving 0.57 parts of calcium acetate monohydrate (0.9 times mole relative to trimethyl phosphate) in 31 parts at room temperature 9.88 1 part and then 0.04 part of antimony trioxide and transferred to a polymerization can. Next, reduce the pressure to 760 mm 1 liter (from I to 1 mml) for 1 hour or c, and at the same time reduce the pressure from 230°C to 285°C over 1 hour and 30 minutes.
The temperature rose to Under reduced pressure of 1 mm and 11 g or less, polymerization temperature 2
Polymerization was continued for 3 hours at 85°C for 814 hours and 30 minutes to obtain a polymer with an intrinsic viscosity of 0.640 and a softening point of 259°C (
F? is. After the reaction was completed, the polymer was made into chips according to a conventional method.

The chips were dried by a conventional method, melt-spun at 290°C using a spinneret with 36 circular spinning holes with a hole diameter of 0.3 mm, wound at 1300 m/min, and drawn into a 40-denier monofilament. A drawn yarn was obtained.

The obtained thread is boiled in a 50% aqueous sodium hydroxide solution according to a conventional method. ! A monofilament fiber whose surface was made microporous with a weight loss rate of 15.2% was obtained by treatment at high temperature.

This is disperse dyed F4Dianix Black tl
G-FS (Mitsubishi Chemical Industries (bead products) 15% owf;
Dispersion and leveling agent Dipper VG (Kasei Chemical Industry ■ product)
pH adjuster, acetic acid 0.3 g/l.

Processing agent A (described later) 10% owf (active ingredient: 1% owf)
After staining with a staining solution containing wf) at 130°C for 60 minutes, it was dried.

Here, processing agent A is dimethyl terephthalic acid and dimethyl terephthalic acid in a molar ratio of 80:20.
Ethylene glycol: A copolymer made by copolymerizing polyethylene glycol (average molecular weight 3100) at a molar ratio of 1:25, and a surfactant made by converting 6 moles of ethylene oxide of nonylphenol into sodium sulfonate are mixed in water. It was adjusted to a 10% dispersion (10% active ingredient).

The obtained black monofilament yarn has an electrical resistance value of 2X1.
08 Ω/cm, and not only had good electrical conductivity due to friction, but also deep black color, heat set durability, mild gloss, and soft tactility.

Comparative example 2 In Example 2, the processing agent A was removed during dyeing.

The obtained non-porous monofilament yarn has an electrical resistance value of 6
1014 Ω/cm, static electricity was generated due to friction, the blackness was insufficient, there was a ``glossy'' appearance, and the feel was poor.

Table 2 shows Example 2. The results of Comparative Example 2 are shown.

Claims (2)

[Claims] (1) Artificial hair made of synthetic fibers, characterized in that the fibers are polyester monofilaments having micropores at least on the fiber surface. (2) In artificial hair made of synthetic fibers, the fibers have at least micropores on the fiber surface, and polyester is coated with an antistatic agent having an electrical resistance value of 10^1^0 Ω/cm or more on the fiber surface. Artificial hair characterized by being monofilament.