JP2002227018A - Artificial hair - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an artificial hair having various required qualities of artificial hair and having good setting properties and hair stylability. SOLUTION: An acrylic polymer composed of 35 to 75% by weight of acrylonitrile, 25 to 65% by weight of a halogen-containing vinyl monomer and 0 to 10% by weight of a vinyl monomer copolymerizable therewith is used. Artificial hair made of fiber, the average circularity of the fiber cross section is 0.8 or more on average, and the average fineness of single fiber is 30 to 100 dtex, has good setting properties, has high hair stylability, and is rich in variety Enable product planning.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to artificial hair used for hair ornaments such as wigs, hairpieces, and weaving, and hair for dolls, and more particularly to hair having good setting properties and hair styling. The present invention relates to a novel artificial hair made of acrylic fiber, which has good hair properties that can produce various hairstyles when the hair is made.

[0002]

2. Description of the Related Art Conventionally, the quality required for artificial hair used for hair ornaments and the like includes appearance such as curl shape, gloss and color development, hair care such as combing and hair stabilization, dyeing, and hackling. There are processing characteristics such as loss and curl setting, or volume, touch, and flame retardancy. Among the currently available hair materials, fibers made of polypropylene or polyester have inferior flame retardancy, and fibers made of vinyl chloride or vinylidene chloride have inferior dyeability or volume per unit weight to other materials. As a material which can satisfy these requirements at the same time, human hair or artificial hair made of acrylic fiber obtained by copolymerizing acrylonitrile and vinyl chloride is known. However, when human hair is used as a material, there are difficulties in obtaining raw materials and hair length. On the other hand, acrylic fibers obtained by copolymerizing acrylonitrile and vinyl chloride also have properties that are balanced in gloss, color development and texture, and have flame retardancy, depending on the product. Since the curl shape changes over time, there is a difficulty in setting the hair. In addition, there is a demand for a hairstyle that cannot be satisfied with the current hair styling of acrylic fibers.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide artificial hair used for hair ornaments and the like, which has good setting properties, has high hair stylability, and is used as a hair material for hair ornaments and the like. An object of the present invention is to provide artificial hair that enables a variety of product planning.

[0004]

Means for Solving the Problems In order to achieve the above-mentioned object, the present inventors have attained various qualities required for artificial hair which acrylic fiber originally has, and at the same time, have acrylic fiber. In order to improve the setting property and hair stabilization, which are the drawbacks of the above, the present invention has been completed by focusing on the cross-sectional structure of the acrylic fiber. That is, the artificial hair according to the present invention comprises 35 to 75% by weight of acrylonitrile, 25 to 65% by weight of a halogen-containing vinyl monomer, and 0 to 10% by weight of a vinyl monomer copolymerizable therewith.
Consisting of fibers using an acrylic polymer consisting of,
The roundness of the fiber cross section is 0.8 or more on average, and the average fineness of a single fiber is 30 to 100 dtex.

[0005] In the present invention, the circular degree of circularity of the fiber section is defined as the fiber width in the fiber section when the distance between two parallel tangents in the fiber section perpendicular to the fiber axis is defined as the fiber width. Means the ratio of the area (F) of the fiber cross section to the area (R) of a circle whose diameter is the maximum width (for example, the distance A between the tangents M ₁ and M ₂ in FIG. 1). This is a value obtained by Expression (1). Circularity = Fiber cross-sectional area / Area of a circle whose maximum width is the diameter ... Equation (1)

By the way, for example, the fiber disclosed in Japanese Patent Publication No. 53-6253 and the fiber disclosed in Japanese Patent Application Laid-Open No. 61-258014 are also made circular. However, these do not have a fineness suitable for artificial hair and do not satisfy the setting properties and hair stabilization required for artificial hair, which is the object of the present invention.

The fiber used for the artificial hair of the present invention is preferably a fiber obtained by a wet spinning method using a spinning solution in which an acrylic polymer is dissolved in a good solvent for the polymer. As a good solvent for the acrylic polymer, it is preferable to use dimethylformamide, dimethylacetamide and dimethylsulfoxide. The halogen-containing vinyl monomer in the acrylic polymer is preferably vinylidene chloride.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The fibers which can be used for the artificial hair of the present invention are fibers comprising an acrylic polymer, 35 to 75% by weight of acrylonitrile, 25 to 65% by weight of a halogen-containing vinyl monomer and the like. 0-10% by weight of copolymerizable vinyl monomer, more preferably 40-70% by weight of acrylonitrile, 30-60% by weight of halogen-containing vinyl monomer and vinyl monomer copolymerizable therewith It is obtained by copolymerizing 0.7 to 8% by weight. 35% by weight of acrylonitrile as a component of the polymer
If it is less than 75%, the heat resistance will be low, resulting in poor settability. Conversely, if it exceeds 75% by weight, the flame retardancy will be poor, and the properties required for hair materials such as hair ornaments will tend to be not satisfied.

As the halogen-containing vinyl monomer, any vinyl monomer containing a halogen atom, preferably a chlorine atom or a bromine atom, can be used. Specifically, vinylidene halide and vinyl halide can be used. Examples of the vinylidene halide include vinylidene chloride and vinylidene bromide, and examples of the vinyl halide include vinyl chloride and vinyl bromide. Among them, a vinylidene halide, particularly a vinylidene chloride is preferable in handling. In addition, when acrylonitrile and vinyl chloride are copolymerized, it is necessary to use a special polymerization vessel compatible with high-pressure gas. On the other hand, in the case of vinylidene chloride, it is possible to produce with a device which does not require such high-pressure gas.
These halogen-containing vinyl monomers may be used alone or in combination of two or more.

The vinyl monomers copolymerizable with the acrylonitrile and the halogen-containing vinyl monomers include, for example, methallyl sulfonic acid, allyl sulfonic acid,
Isoprenesulfonic acid, styrenesulfonic acid and 2-
Sulfonic acid group-containing vinyl monomers represented by acrylamide-2-methylpropanesulfonic acid and the like, or sodium, potassium and ammonium salts thereof, and lower alkyl esters such as methyl, ethyl, propyl and butyl of acrylic acid and methacrylic acid. Carboxyl group-containing vinyl monomers such as lower alkyl esters and glycidyl esters of vinyl group-containing carboxylic acids, acrylamide, methacrylamide and their N-alkyl substituents, acrylic acid, methacrylic acid and itaconic acid; These sodium, potassium and ammonium salts, vinyl acetate and the like,
It is not limited to these. These may be used alone or in combination of two or more. Among these various vinyl monomers, in the case of a sulfonic acid group-containing vinyl monomer, the composition in the polymer is required in order to make the effect of densification and rounding of the cross section of the fiber remarkable during wet spinning. The proportion is preferably at least 0.7% by weight, more preferably at least 1.5% by weight. However, if the composition ratio of the sulfonic acid group-containing vinyl monomer in the polymer is too large, the solubility of the polymer when dissolved in a solvent may decrease or the resulting solution (spun stock solution) may increase in viscosity. Fiberization may be difficult, and if it exceeds 5% by weight, the fiber formation process by wet spinning may be adversely affected, which is not preferable.

The acrylonitrile, the halogen-containing vinyl monomer and the vinyl monomer copolymerizable therewith can be copolymerized to obtain a polymer by a usual vinyl polymerization method, for example, a slurry polymerization method, an emulsification method, or the like. Any method such as a polymerization method and a solution polymerization method may be used, and there is no particular limitation.

The above acrylic polymer is dimethylacetamide (hereinafter, referred to as DMAc), dimethylformamide (hereinafter, referred to as DMF), dimethylsulfoxide (hereinafter, referred to as DMSO) which is a good solvent for acetone or acrylic polymer. ) Can be dissolved into a solvent to prepare a spinning solution and wet-spun to form a fiber. It is preferable to wet-spun using a good solvent such as DMAc, DMF or DMSO as the solvent.

The concentration of the stock solution depends on the degree of polymerization of the polymer and the composition ratio of the copolymer, but is generally adjusted to 20 to 35% by weight, and the viscosity of the stock solution is measured at 40 ° C. using a rotational viscometer (B-type viscometer). It is preferable in terms of handling that the measured value is 30 to 800 dPa · sec, and furthermore, 50 dPa · sec or more, more preferably 150 dPa · sec from the aspect of the circular solidity of the fiber cross section.
dPa · sec or more.

Further, when a stock solution prepared by containing water in an amount of 5 to 20% of the weight of the polymer is used as a stock solution for spinning, the solidification rate of the polymer becomes slow, and the generation of macrovoids during wet spinning is reduced. It is more preferable in the process because the fiber having a reduced cross section and a more uniform fiber shape having a high degree of roundness is obtained, and the content of residual solvent in the fiber after washing is reduced. When the amount of water added is less than 5%, the circular solidity of the fiber cross section tends to decrease as the amount of water added decreases, but there is no particular problem if the circular solidity reaches the target value. On the other hand, if the added amount of water exceeds 20%, gelling of the spinning dope tends to occur and the stability of the stock solution tends to be deteriorated, which is not preferable since troubles in fiber production increase.

The spinning dope may be appropriately added with a stabilizer for preventing the coloring of the stock, light and heat resistance, a dye improver, a coloring agent for artificial hair, a gloss regulator and the like in view of the practicality of the fiber. .

The spinning is preferably performed by a wet spinning method using an aqueous solution of the solvent used for preparing the stock solution as a coagulation bath. In order to make the fiber cross section dense and increase the degree of circular filling, it is preferable that the orifice is spun through a spinning nozzle having a circular shape at a spinning nozzle draft of about 0.3 to 1.2. As the coagulation condition, generally, a condition in which the coagulation speed is slow is adopted, but the coagulation bath temperature, the coagulation bath concentration, or the stock solution preparation conditions are appropriately set depending on the type of the solvent or the polymer composition.

For example, a copolymer in the range of 35 to 55% by weight of acrylonitrile, 65 to 45% by weight of a halogen-containing vinyl monomer and 0 to 3% by weight of a sodium sulfonate-containing vinyl monomer is dissolved in acetone and wet-processed. When spinning, the temperature is usually 20 to 30 ° C, and the acetone concentration is 20 to 30.
The desired circularity can be obtained by spinning the fiber into an aqueous solution of 50% by weight under a spinning condition of a temperature of 15 ° C. or less and an acetone concentration of 50 to 75% by weight.

When a solvent such as DMAc, DMF or DMSO which is positioned as a better solvent than acetone is used, an acrylic polymer obtained by copolymerizing 55% by weight or more of acrylonitrile, whose solubility in acetone is reduced, is also dissolved. can do. In this case, by using a stock solution prepared by adding 5 to 20% of the weight of the polymer to water as described above, the occurrence of macrovoids is reduced, and fibers having a more uniform circular cross section are obtained. This is preferable because the content of the residual solvent in the obtained fibers after washing with water decreases. In this case, the coagulation bath preferably has a temperature of 10 to 40 ° C. and a concentration of 30 to 70% by weight.

The acrylic polymer spun and fiberized as described above is then treated with an aqueous solution having a lower solvent concentration of 30 ° C. or higher, warm water at 40 to 60 ° C., and 60 ° C.
It is led to a washing bath composed of hot water or boiling water at a temperature of not less than ° C, and is subjected to desolvation, stretching, and, if necessary, relaxation treatment. The total stretching ratio at this time is preferably 2 to 10 times, more preferably 3 to 8 times, and the stretching may be divided and distributed. Next, the process oil is applied and dried. The process oil is used for the purpose of preventing static electricity, preventing sticking of fibers and improving texture, but known oil components are sufficient. The dried fiber is then further stretched if necessary, but the draw ratio is 1
~ 4 times. The fiber obtained by drying or drawing is
Further, a relaxation treatment is performed in a high-temperature dry heat atmosphere or a pressurized steam atmosphere to obtain a desired fiber. The relaxation rate is usually from 8 to 35%, and more preferably from 13 to 30%, depending on the stretching ratio.

The fineness of the single fiber is preferably 30 to 100 dtex, more preferably 40 to 80 dtex, because it is a hair material.
If it is less than 30 dtex, the hair is too thin and loses volume, resulting in an unnatural hairstyle and 100 dt
If the value of ex is exceeded, the hair will have a strong hardness and lack flexibility in the movement of the hair, resulting in a rough hair such as a needle mouse.

In order to remarkably improve the curl development of a single fiber, it is preferable that the average degree of circularity of the fiber cross section is 0.8 or more from the viewpoint of the balance between curl retention, that is, setability and hair stabilization. More preferably, it is 0.85 or more. If the degree of circularity is less than 0.8 (for example, an elliptical to flat cross-sectional shape), the heat-set curl will have a large elongation due to its own weight, making it difficult to obtain the desired curl. In addition, if only the curl manifestation is improved, there are some which can achieve the purpose even with a Y-shaped or cross fiber cross-sectional shape having a circular fulfillment of less than 0.8, but there is a rough feeling and rough feeling on the tactile sensation, As a result, hair quality is deteriorated, resulting in a loss of quality balance, which is not preferable as hair characteristics. Therefore, circular artificialness is an important factor for artificial hair balanced in setting properties and hair stylability. However, a structure such as an O-shaped cross section having a hollow structure at the center of the fiber cross-section or a C-shaped cross-section having a cavity at the center where the flat cross-section is deformed is out of the scope of the solid fiber cross-section targeted by the present invention. . Further, when there is a concave portion on the outer periphery of the fiber cross section, as shown in FIG. 1, the distance from the tangent (N ₁ ) closest to the concave portion (H) and not crossing the fiber cross section to the deepest portion of the concave portion (H) is shown. shortest distance (b), the tangents (N ₁₎ and the該接line (N ₁₎ ratio another tangent parallel fiber width length sandwiched by (N ₂₎ (B) to (%) depressions of h Then, the degree of depression h (%) may be 20% or less. In addition,
The dent degree h (%) is obtained by the following equation (2). Depression degree: h (%) = 100 × (b / B) Equation (2) The reason is that, for example, if a large cavity or dent exists inside the fiber cross section such as an O-shaped cross section or a C-shaped cross section, This is because fibers are easily broken, crushed, fibrillated, and the like due to external forces such as shampooing and combing, and the quality as a hair material is reduced.

The artificial hair of the present invention as described above can be used, for example, for hair ornaments such as wigs, hairpieces, and weaving, and hair for dolls, and in particular, hair ornaments that require setability and hairstyling. It can be suitably used for example.

[0023]

EXAMPLES Hereinafter, the present invention will be further described based on examples and comparative examples, but the present invention is not limited to these examples. In the following description, all percentages of the chemical composition indicate weight%. Prior to the description of the examples, preparation methods and evaluation methods of evaluation samples will be described below.

(Fineness) Motorcycle blow type fineness measuring device DEN
The measurement was performed using an IER COMPUTER type DC-11 (manufactured by Search Co., Ltd.), and the average value of the sample number n = 30 was determined.

(Circularity) A fiber bundle having a diameter of about 2 mmφ was fixed with an epoxy adhesive, and cut in a direction perpendicular to the fiber bundle to prepare several samples for fiber cross-section observation. The sample cuts the cut surface of the fiber bundle with an ion coater IB
-3 type (manufactured by Eiko Engineering Co., Ltd.) after Au deposition, then scanning electron microscope S-3500N type (Co., Ltd.)
Using Hitachi, Ltd.), a fiber cross-section photograph was taken, and the maximum width (A) and area (F) of each fiber cross-section were measured as shown in FIG. The circular fulfillment was determined, and the average value of the number of fiber cross-section samples n = 20 was determined. The maximum width length (A) and area (F) of the fiber cross section
Is the image processing software Image-Hyper II
(Interquest Co., Ltd.). Circularity = (Fiber cross-sectional area / Area of a circle whose diameter is the maximum width) Equation (1) = 4F / (A ² π)

(Setting property) The fiber bundle is cut to a fiber length of 45 cm, sewn at a distance of 20 cm from the end of the fiber with a mino hair forming sewing machine, and the seam is turned back to obtain a hair length of about 24 cm.
Created mino hair. Next, the mino hairs cut to a width of 12 cm are spread on a paper and straightened with a comb. The hairs are wrapped around the outer circumference of an aluminum pipe having a diameter of 32 mm so that the paper is concentrically wound. ,
The heat set was carried out for 60 minutes and removed. Then cool naturally to room temperature, remove the mino hair from the aluminum pipe,
After hanging for days, the hair length from the seam portion to the tip of the curl was measured to determine the setting. The shorter the measured hair length, the better the setting.

(Hair Stylability) Straight mino hairs prepared in the same manner as described above were sewn on a non-stretchable net cloth at 10-step intervals at intervals of 1 cm. Card,
The hairstyle including the appearance of the curl shape was observed. The evaluation was made by five wig engineers including a hairdresser based on the following criteria, and the average value was adopted. Evaluation criteria of hair scalability A: As a result of smooth curl waves, a three-dimensional effect can be expressed and a hairstyle can be arranged. ：: As a result of the curl waves being relatively relatively untouched, a three-dimensional effect can be expressed and the hairstyle can be adjusted. ×: Unless time and effort are taken, curl waves cannot be prepared and hairstyles are difficult to prepare.

Example 1 Acrylonitrile 57.0
%, 41.5% of vinylidene chloride and 1.5% of sodium methallylsulfonate are dissolved in DMF.
12% water was added to the polymer, mixed and dissolved.
Further defoamed, 28% concentration, viscosity at 40 ° C 3
A 90 dPa · s spinning stock solution was passed through a spinning nozzle having a circular hole shape (50 holes, hole diameter 0.28 mm) at 15 ° C.
It was spun into a coagulation bath consisting of a 60% strength by weight DMF aqueous solution. Then, it was introduced into a bath composed of a 30% by weight aqueous solution of DMF at 45 ° C., stretched twice, and further stretched at 70 ° C. and 15% by weight D
Stretch 1.5 times in a bath composed of an aqueous MF solution,
The film was stretched by a total of three times through a hot water bath at ℃ and washed with water.
Next, after the process oil agent was adhered, it was dried with a hot air dryer at 145 ° C., stretched twice, and heat-treated at 160 ° C. Thereafter, a relaxation treatment of 21% under tension was performed in a 0.27 MPa steam atmosphere. The obtained fibers had a single yarn fineness of 57 dtex and a circular cross-section of 0.9 in the fiber cross section.
3. The degree of dent was 3% or less. Table 1 shows the results of preparing and evaluating mino hair using this fiber.

(Comparative Example 1) The copolymer composition was changed to acrylonitrile 57.0%, vinylidene chloride 42.6%, sodium methallylsulfonate 0.4%, and the DMF solution of the polymer to which water was not added. Except that
A fiber was prepared according to Example 1. The obtained fiber had a single yarn fineness of 57 dtex and a circular cross-section of the fiber cross section of 0.7 d.
0 and the degree of dent was 3% or less as in Example 1. Table 1 shows the results of preparing and evaluating mino hair using this fiber.

Example 2 Acrylonitrile 48.8
% Of vinylidene chloride and 1.2% of sodium styrenesulfonate are dissolved in DMAc, and 10% by weight of water is added to the polymer to give a concentration of 30% by weight, 40 ° C. To obtain a spinning solution having a viscosity of 60 dPa · s. The spinning stock solution was passed through a spinning nozzle having a circular hole shape (50 holes, hole diameter: 0.30 mm) at 18 ° C. and a concentration of 67.
It was spun into a coagulation bath consisting of a weight percent DMAc aqueous solution. Next, the film is stretched 1.6 times in a bath composed of a 20% by weight aqueous DMAc solution at 20 ° C., and then 1.9 times stretched through a 50 ° C., 90 ° C. water washing bath to adhere the process oil. 1
Dried at 20 ° C. Subsequently, the film was stretched 2.5 times at the same temperature, and after a relaxation treatment of 3% at 145 ° C., 0.22 MPa
20% relaxation treatment under tension in a pressurized steam atmosphere. The obtained fiber had a single yarn fineness of 55 dtex, a roundness of the fiber cross section of 0.85, and a dent degree of 6%. Table 1 shows the results of preparing and evaluating mino hair using this fiber.

Comparative Example 2 Fibers were prepared in the same manner as in Example 2 except that the copolymer composition was 49.5% of acrylonitrile, 50.0% of vinylidene chloride, and 0.5% of sodium styrenesulfonate. The obtained fiber has a single yarn fineness of 55.
The dtex, the degree of circular roundness of the fiber cross section was 0.75, and the degree of depression was 17%. Table 1 shows the results of preparing and evaluating mino hair using this fiber.

Example 3 Acrylonitrile 49.0
% Of vinyl chloride, 50.0% of vinyl chloride, and 1.0% of sodium styrenesulfonate dissolved in acetone. A spinning dope having a concentration of 30% by weight and a viscosity of 50 dPa · s at 40 ° C. Spinning nozzle with a circular shape (50 holes,
The mixture was spun through a coagulation bath consisting of a 70% acetone aqueous solution at 10 ° C. through a pore diameter of 0.35 mm). Then 20 ° C, concentration 4
The film was stretched 1.6 times in a bath composed of 0% by weight acetone aqueous solution, and then the process oil was applied thereto through a 50 ° C. water-washing bath, then dried at 120 ° C. and stretched 2.5 times. rear,
A 10% relaxation heat treatment was performed at 145 ° C. The obtained fiber had a single-fiber fineness of 55 dtex, a roundness of fiber cross section of 0.85, and a dent degree of 3% or less. Table 1 shows the results of preparing and evaluating mino hair using this fiber.

Comparative Example 3 Fibers were prepared in the same manner as in Example 3 except that the initial coagulation bath conditions among the spinning conditions used in Example 3 were changed to an aqueous acetone solution having a concentration of 20 ° C. and a concentration of 20% by weight. . The single fiber fineness of the obtained fiber was 55 dtex, the circular solidity of the fiber cross section was 0.67, and the degree of dent was 53%. Table 1 shows the results of preparing and evaluating mino hair using this fiber.

[0034]

[Table 1]

As is evident from the results in Table 1, acrylic fibers having a circular cross section of 0.8 or more in fiber cross section have good setting properties and high hair stylability when used as artificial hair. .

[0036]

Industrial Applicability The present invention has various required qualities as artificial hair used for hair ornaments and the like, and in particular, has excellent setting properties and hair stylability, which are disadvantages of acrylic fibers, and provides various hair styles. It can be easily made and a variety of products such as hair ornaments can be planned.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing a method for measuring the degree of circular solidity and the degree of depression of a concave portion in a fiber cross section.

[Explanation of symbols]

A: Maximum width of fiber cross section, B: Fiber width length, b: Shortest distance from the innermost part of recess to nearest tangent line, F: Area of fiber cross section, H: recess, M ₁ , M ₂ : parallel Tangents, N ₁ , N ₂ : parallel tangents, R: area of a circle whose diameter is the maximum width of the fiber cross section.

Claims (4)

[Claims] 1. An acrylic polymer comprising 35 to 75% by weight of acrylonitrile, 25 to 65% by weight of a halogen-containing vinyl monomer and 0 to 10% by weight of a vinyl monomer copolymerizable therewith. Synthetic hair comprising a fiber having a circular cross-section of 0.8 or more on average and a single fiber having an average fineness of 30 to 100 dtex. 2. The artificial hair according to claim 1, wherein the fiber is a fiber obtained by a wet spinning method using a spinning solution obtained by dissolving an acrylic polymer in a good solvent for the polymer. 3. The method according to claim 1, wherein the good solvent is dimethylformamide,
The artificial hair according to claim 2, wherein the artificial hair is at least one member selected from the group consisting of dimethylacetamide and dimethylsulfoxide. 4. The artificial hair according to claim 1, wherein the halogen-containing vinyl monomer is vinylidene chloride.