JPH09324315A - Polyester artificial hair and method for producing the same - Google Patents

Abstract

(57) [PROBLEMS] To provide a polyester artificial hair which has excellent flame retardancy and bathochromic properties and is resistant to fading to light. SOLUTION: For example, polyester artificial hair made of polyester having a glass transition temperature of 35 to 60 ° C., which is obtained by copolymerizing an aliphatic dicarboxylic acid or the like with polyethylene terephthalate in an amount of 5 to 20 mol%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to polyester artificial hair. More specifically, the present invention relates to a polyester artificial hair that has properties such as sufficient flexibility, setting properties, heat resistance, and light resistance, and can also exhibit excellent flame retardancy and bathochromic properties, and a method for producing the same.

[0002]

2. Description of the Related Art As a material for artificial hair used in wigs, hair wigs, hair attachments, hair bands and the like, modacrylics have been widely used due to their characteristics such as flame retardancy. However, since modacrylic is insufficient in setting properties, polyethylene has recently been excellent in setting properties (easy to set and good holding property), less fading to light, and good properties such as tensile strength and heat resistance. Fibers whose main component is polyester represented by terephthalate have come to be used.

However, when polyester fibers such as polyethylene terephthalate are used as they are as artificial hair, they have problems such as insufficient flame retardancy and insufficient bathochromicity, that is, depth of color. Is restricted.

Conventionally known methods for imparting flame retardancy to polyester fibers include a method of copolymerizing a polyester polymer with a flame-retardant monomer containing a phosphorus atom, a method of exhausting a flame retardant to a polyester fiber, and the like. ing. As the former method for copolymerizing a flame-retardant monomer, for example, JP-B-55-41610 discloses a method for copolymerizing a phosphorus compound having a phosphorus atom as a ring member and having good thermal stability. Japanese Patent Publication No. 53-13479 proposes a method of copolymerizing carboxyphosphinic acid. On the other hand, as the latter method of exhausting the flame retardant, Japanese Patent Publication No. 3-57990 discloses a method of exhausting finely divided halogenated cycloalkane compounds into polyester fibers, and Japanese Patent Publication No. 1-291313 discloses. A method of exhausting alkylcyclohexane containing a bromine atom has been proposed.

As the application of these flame-retardant techniques to artificial hair, polyester fibers copolymerized with phosphorus compounds have been proposed, for example, in Japanese Patent Laid-Open Nos. 3-27105 and 5-339805. ing. However, since artificial flame requires high flame retardancy, the amount of copolymerization of these copolyesters must be increased in order to use them in artificial hair. There is a problem in that the yarn is drastically reduced and it becomes difficult to make yarn.

On the other hand, in the above method of exhausting the flame retardant into the polyester fiber, in order to increase the exhaust amount,
For example, it is necessary to set the exhaustion treatment temperature to a high temperature of 150 ° C. or higher, the treatment time needs to be a long time ignoring the productivity, or a large amount of flame retardant in which the flame retardant is not exhausted. However, there is a problem that the physical properties of the fiber are impaired and the cost of the artificial hair becomes extremely high.

[0007] Another required characteristic of artificial hair is luster and bathochromicity, which requires a high dye exhaustion amount.

As described above, it is required that the dye and the flame retardant are simultaneously exhausted (or copolymerized) in a high amount in the artificial hair. In response to these requirements, the conventional polyester artificial hair is used. Had not reached a satisfactory level.

On the other hand, in order to easily exhaust the modifiers such as dyes and flame retardants, various methods have been proposed for changing the fiber structure to lower the degree of orientation of the amorphous part. The improvement of exhaustion is insufficient. A method of copolymerizing the third component to facilitate exhaustion of the modifier has also been proposed,
Its properties vary greatly depending on the type of the copolymerization component, and it has not yet been found that it can be used as an artificial hair by satisfying the exhaustiveness of the dye and the properties such as mechanical properties, heat resistance and light resistance at the same time. It has not been. That is, if the amount of copolymerization is simply increased to improve the exhaustivity of the dye, the melting point is significantly lowered, the heat resistance becomes insufficient, and a problem such as fusion tends to occur. On the other hand, if polyoxyalkylene glycol having a molecular weight of several thousand such as polyethylene glycol is copolymerized to improve the exhaustion property while keeping the melting point high, the light resistance is poor and the color easily fades during use, causing a feeling of tiredness. There was a problem.

As described above, polyester-based artificial hair which is excellent in flame retardancy, bathochromic property, and fading to light, and which is excellent in easy-to-set property and set-retaining property, which are characteristics of polyester, has not yet been obtained. Is the current situation.

[0011]

SUMMARY OF THE INVENTION The present invention has been made against the above background, and an object thereof is to have excellent flame retardancy and bathochromic property, and also to have characteristics that fading to light is difficult. It is intended to provide a polyester artificial hair and a method for producing the same.

[0012]

In order to achieve the above-mentioned object, the present inventors have studied the exhaustion (adsorption) of modifiers such as flame retardants and dyes, and particularly the factors affecting the exhaustion rate. As a result of diligent studies, it was found that it is not enough to loosen the structure of the amorphous portion of the polyester fiber (low orientation), and the ease of movement of the molecular chain itself of the amorphous portion is an important factor. Reached

That is, according to the present invention, "polyester artificial hair made of polyester having a glass transition temperature of 35 to 60 ° C." is provided, and "fiber made of polyester having a glass transition temperature of 35 to 60 ° C." The 110
A method for producing a polyester artificial hair, which is capable of exhausting 2% by weight or more of a dye and 2% by weight or more of a flame retardant by simultaneously performing dyeing and flame retardant exhaustion processing at a temperature of 140 ° C. Is provided.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester constituting the artificial hair of the present invention has a glass transition temperature of 35 to 60 in order for the flame retardant and dye in the fiber to move at a sufficient diffusion rate.
It is necessary to be in the range of 40 ° C, preferably 40 to 55 ° C. When the glass transition temperature exceeds 60 ° C., it becomes difficult to sufficiently move the agent within the fiber without impairing the mechanical properties of the fiber, and thus the agent cannot be exhausted in a sufficient amount. . On the other hand, the glass transition temperature is 35
If the temperature is lower than 0 ° C, the agents are sufficiently exhausted, but during use of the artificial hair, these agents bleed out to the fiber surface, which is disadvantageous in that they are easily decomposed due to sunlight or the like and faded. Not noticeable because it stands out.

Next, the polyester having the above glass transition temperature will be described. Conventional flame resistance, dyeability,
In order to improve other properties, various polyesters, particularly polyesters obtained by copolymerizing polyethylene terephthalate with a third component, have been disclosed. For example, polyesters obtained by copolymerizing a monomer containing a phosphorus atom to impart flame retardancy are disclosed in JP-B-55-41610 and JP-B-53-53.
It is disclosed in Japanese Patent No. 13479 and the like, and it is also disclosed in Japanese Patent Application Laid-Open No. 3-27105, Japanese Patent Application Laid-Open No. 5-339805 and the like that artificial hair is made from such polyester. However, if the copolymerization ratio of these polyesters is excessively increased, the heat resistance is significantly lowered, so that it is difficult to set the copolymerization amount to 5 mol% or more, and the glass transition temperature is lowered to about 65 ° C at most. Not not. Therefore, even if an attempt was made to exhaust the flame retardant for the purpose of imparting sufficient flame retardancy as artificial hair, the amount of exhaustion was insufficient.

On the other hand, the isophthalic acid component, which is often copolymerized with polyethylene terephthalate, does not lower the rigidity of the polymer chain obtained so much, so that the glass transition temperature of the obtained copolyester does not decrease so much.

Therefore, in the present invention, the copolymerization component is preferably an aliphatic component having a good molecular chain mobility, and particularly α, ω-polymethylene diol or dicarboxylic acid (a part of the methylene group is a hetero atom such as oxygen). Optionally substituted by atoms) is preferred. Specifically, preferred examples include diethylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid. Of these, the dicarboxylic acid component is more
It is more preferable because the problem of scattering into a vacuum system in the polyester polymerization reaction is less likely to occur, and adipic acid is particularly preferable because it has excellent industrial properties of the obtained artificial hair and is low in cost, and thus has great industrial value. Polyester terephthalate is preferably used as the polyester to be copolymerized, and polyalkylene terephthalate using a glycol having a long methylene chain, such as polybutylene terephthalate, achieves the object of the present invention because the glass transition temperature becomes too low. I can't.

If the copolymerization amount of such a copolymerization component is too small, the glass transition temperature cannot be lowered sufficiently, so that it is 5 based on the total acid component of the polyester.
A range of -20 mol% is suitable. Copolymerization amount is 5 mol%
If it is less than 60 ° C, it is difficult to lower the glass transition temperature to 60 ° C or lower, while if it exceeds 20mol%, the glass transition temperature tends to be less than 35 ° C, and the melting point of the copolyester is 200 ° C. In the following cases, heat resistance becomes insufficient, and defects such as fusion of fibers are likely to occur.

The glass transition temperature can be lowered by copolymerizing a linear polyoxyalkylene glycol such as polyethylene glycol having an average molecular weight of about 400 to 4000. However, the polyester referred to in the present invention does not include such a block copolymer having a polyether chain introduced therein. In the polyether ester block copolymer, when the glass transition temperature is lowered to a desired value, the properties of polyoxyalkylene glycol,
That is, it is inferior in light resistance, so that it easily fades during use, and it easily causes a tired feeling.Because it is inferior in chemical resistance, its properties are easily changed by sprays and cosmetics for hair. It is not preferable because it has drawbacks such as exhaustion.

The above-mentioned polyester according to the present invention is preferably not copolymerized from the viewpoint of not lowering the melting point (heat resistance) except for the copolymerization component for lowering the glass transition temperature, but the object of the present invention is As long as it does not inhibit, components such as isophthalic acid and 5-sodium sulfoisophthalic acid may be copolymerized, and further, a matting agent, an antistatic agent, a cationic dyeing agent, an ultraviolet absorber, an antioxidant. You may mix | blend various additives, such as.

In the present invention, the artificial fibers are prepared by exhausting the dye and flame retardant into the fibers made of the above polyester. At this time, the exhaust amount of the dye and the flame retardant is preferably 2% by weight or more, and particularly preferably 3% by weight or more based on the weight of the fiber in order to satisfy sufficient bathochromic property and flame retardancy. On the other hand, the upper limit of these exhaust amounts is not particularly limited, but if the amount is too large, no further effect will be expressed, so the former amount is usually 10% by weight or less,
It is desirable that the latter be 7.5% by weight or less.

The dye used here may be any color such as black, brown and yellow, and may be appropriately selected according to the desired color. Also, the flame retardant is not particularly limited, and those conventionally used for flame retarding polyester are used. For example, phosphorus-based flame retardants, halogen-containing phosphorus-based flame retardants, halogenated cycloalkane-based flame retardants, and the like can be cited. Among them, halogenated cycloalkane-based flame retardants, specifically hexabromocyclododecane (HBC
D) is preferred.

Further, the concentration distribution (M _in / M _ave ) of the flame retardant in the fiber is preferably 0.2 or more, particularly 0.4 or more. When this concentration distribution is less than 0.2, the flame retardant effect tends to be difficult to sufficiently develop even if the amount of the flame retardant exhausted with respect to the fiber weight is large. In addition, M _in represents the exhaust concentration of the flame retardant in a portion at a distance of 10 μm or more from the surface of the artificial hair, and M _ave represents the average exhaust concentration of the flame retardant in the entire artificial hair.

In order to exhaust the dye and the flame retardant to the polyester fiber, they may be treated in different treatment baths, but it is preferable to treat them in the same bath from the viewpoint of work, equipment, cost and the like. The treatment temperature is 110 to 140 ° C., preferably 120 to 130 ° C. At a temperature higher than this range, it is easy to increase the amount of exhausted agent, but mechanical properties such as strength are likely to decrease, and conversely at a low temperature. The exhaustion amount of the agent and the concentration distribution of the flame retardant tend to be insufficient. Since the polyester used in the present invention has a glass transition temperature within the specific range as described above, even if the same bath treatment is performed for dyeing and flame retardant exhaust treatment, the dye exhaust amount and flame retardant exhaust amount thereof It is possible to be within the range at the same time, and the flame retardant concentration distribution also satisfies the above, excellent uniformity,
A polyester artificial hair having good flame retardance and bathochromism can be obtained. On the other hand, conventional flexible component polyesters such as polyethylene terephthalate in which the flexible component is not sufficiently copolymerized, if the dyeing and the flame retardant exhaustion treatment are simultaneously performed, the exhaustion amount of the dye or the flame retardant is insufficient, Further, it is difficult to set the concentration distribution of the flame retardant to 0.2 or more.

[0025]

EXAMPLES The present invention will be described below more specifically with reference to examples.

[Preparation of Flame Retardant] 100 g of hexabromocyclododecane (HBCD), 20 g of sodium dodecylated diphenyl ether sulfonate (Difax 2A, manufactured by Dow Chemical Co.) as a dispersant, and 60 g of water were mixed and mixed sufficiently. Predisperse until fluidity. This pre-dispersed liquid was added to 250 g of ceramic particles (diameter 0.3-
It was pulverized in a bead mill having a diameter of 1.2 mm), and the obtained dispersion was mixed with a 5 wt% aqueous solution of carboxymethyl cellulose and water to prepare a 45 wt% HBCD dispersion. The content concentration of carboxymethyl cellulose was 0.9% by weight. This dispersion was diluted 100 times with water, trace amounts were collected on a glass plate and dried, and then silver vapor deposition was performed to take a scanning electron microscope photograph, and a magnification was 500.
When the particle size was measured from a double photograph, the average particle size was 1.8 μm.

Example 1 In a transesterification reactor, 8.48 Kg (43.75 mol) of dimethyl phthalate, 1.09 Kg (6.25 mol) of dimethyl adipate, 5.58 Kg (90 mol) of ethylene glycol and tetramanganese acetate 4.5 g of hydrate was added and the mixture was heated to 140 ° C. under a nitrogen atmosphere with stirring. The reaction temperature was raised to 230 ° C. over 4 hours, and desorbed methanol and excess ethylene glycol were distilled off. Next, the molten reaction product was transferred to a polycondenser, and 0.9 g of phosphoric acid and 5.5 of antimony trioxide were added.
and g were mixed, and ethylene glycol was distilled off under a weak reduced pressure at 240 ° C. under a nitrogen atmosphere.

Then the internal pressure is still reduced over a period of 1 hour by 1.3 mbar and the temperature of the melt is from 240 ° C. to 2 °
The temperature was gradually raised to 70 ° C. After raising the temperature to 280 ° C. over a further 30 minutes, the intrinsic viscosity of the melt was 0.
Polymerization was carried out with further stirring until it reached 7.

The polyethylene phthalate copolymer polyester (glass transition temperature 50 ° C.) thus obtained was once made into chips. After drying this, it was supplied to an extruder and melted at a temperature of 285 ° C. Then, the molten polymer was discharged using a spinneret having a round cross-section nozzle hole with a diameter of 0.8 mm, cooled in a hot water bath at a temperature of 60 ° C. installed at a position 20 cm below the spinneret, and subsequently air-cooled, and then once. It was wound up to obtain a spun yarn. This spun raw yarn was drawn in one step in a warm water bath at a temperature of 95 ° C. and then drawn while being heated by a non-contact heater to obtain a drawn yarn for artificial hair having a single yarn fineness of 50 denier.

A shackle is formed with the obtained drawn yarn for artificial hair,
Sumikaron Navy Black S-2GL 15% ow as a dye
f, and 9% owf (H
(As BCD), was immersed in a treatment liquid having a bath ratio of 1:20, and treated at 130 ° C. for the time shown in Table 1 using a high-pressure dyeing machine. Next, reduction rinsing is performed for 20 minutes at a bath ratio of 1:20 and a temperature of 80 ° C. in an aqueous solution containing 1.5 g of hydrosulfite, 1 g of caustic soda and 1 g of amylazine in 1 liter of water, and dyed drawn yarn (artificial hair). Got

The obtained dyed drawn yarn was dissolved in orthochlorophenol and the absorbance was measured by a colorimeter to determine the concentration of the dye exhausted in the fiber. Further, the dyed drawn yarn was made into powder, and 100 mg thereof was compression-molded, and this was subjected to fluorescent X-ray analysis to determine the content of bromine atoms, and the HBCD exhaust amount was calculated from this. On the other hand, regarding the concentration of the flame retardant in the cross-sectional direction of the dyed drawn yarn, XMA
The distribution of bromine atoms in the fiber cross-sectional direction was measured by measurement, and M _in / M _ave was determined from this distribution.

Regarding the flame retardancy, a dyed drawn yarn having a length of 10 cm was installed vertically, and the lower end thereof was ignited by a burner to measure the carbonization length. For artificial hair,
The carbonization length is required to be 3 cm or less. The results are shown in Table 1.

[0033]

[Table 1]

Comparative Example 1 9.70 Kg (50 mol) of dimethyl phthalate, 5.58 Kg (90 mol) of ethylene glycol and 4.5 g of manganese acetate tetrahydrate were charged into a transesterification reactor, and the mixture was placed in a nitrogen atmosphere. Heated to 140 ° C. with stirring underneath. Reaction temperature is 2 over 4 hours
The temperature was raised to 30 ° C., and desorbed methanol and excess ethylene glycol were distilled off. Next, the molten reaction product was transferred to a polycondenser, 0.9 g of phosphoric acid and 5.5 g of antimony trioxide were mixed, and ethylene glycol was distilled off at 240 ° C. under a nitrogen atmosphere under a slight reduced pressure. In the same manner as above, polymerization was carried out until the intrinsic viscosity became 0.7, and then the chips were once made. The glass transition temperature of the obtained polymer is 6
9 ° C.

After the chips were dried, they were fed to an extruder and melted at a temperature of 295 ° C. Then diameter 0.8
The molten polymer was discharged using a spinneret having a circular cross-section nozzle hole of mm, cooled in a warm water bath at a temperature of 60 ° C. installed 20 cm below the spinneret, and subsequently air-cooled,
It was once wound to obtain a spun raw yarn. This spinning yarn is heated to a temperature of 95
After performing one-stage drawing in a warm water bath at ℃, it was further drawn while heating with a non-contact heater to obtain a drawn yarn for artificial hair having a single yarn fineness of 50 denier.

The drawn yarn thus obtained was subjected to dyeing / flame retardant exhaustion treatment in the same manner as in Example 1, and the same evaluation was carried out. Table 2 shows the results.

[0037]

[Table 2]

[Examples 2-4, Comparative Examples 2-3] Example 1
In, a drawn yarn for artificial hair was obtained in the same manner as in Example 1 except that the copolymerization amount of adipic acid was changed as shown in Table 3. The drawn yarn was subjected to dyeing / flame retardant exhaustion treatment in the same manner as in Example 1 (treatment time was 135 minutes), and the same evaluation was performed. The results are shown in Table 3 together with the results of Example 1 and Comparative Example 1.

[0039]

[Table 3]

[0040]

EFFECT OF THE INVENTION Since the artificial hair of the present invention is made of polyester, it has the same excellent settability, heat resistance, light resistance, etc. as before, and has a glass transition temperature within the above specified range. It is possible to easily exhaust a sufficient amount of flame retardants and dyes, and it is possible to achieve sufficient flame retardancy and bathochromic properties required for artificial hair, and it is also excellent with excellent flexibility. It is a thing.

Claims (5)

[Claims] 1. A polyester artificial hair, characterized by comprising a polyester having a glass transition temperature of 35 to 60 ° C. 2. The polyester artificial hair according to claim 1, wherein the polyester is a polyethylene terephthalate copolymer polyester obtained by copolymerizing an aliphatic dicarboxylic acid component with 5.0 to 20.0 mol% with respect to all acid components. 3. The polyester artificial hair according to claim 2, wherein the aliphatic dicarboxylic acid is adipic acid. Wherein is flame retardant is exhaust, polyester artificial hair according to claim 1, the concentration distribution M _in / M _ave of the flame retardant is at least 0.2. However, M _in represents the exhaustion concentration of the flame retardant in the portion at a distance of 10 μm or more from the surface of the artificial hair, and M _ave represents the average exhaustion concentration of the flame retardant in the entire artificial hair. 5. A dye made of polyester having a glass transition temperature of 35 to 60 ° C. at a temperature of 110 to 140 ° C. and a flame retardant exhaustion process at the same time to obtain 2% by weight or more of a dye, and A method for producing a polyester artificial hair, which comprises exhausting 2% by weight or more of a flame retardant.