JP3130982B2 - Animal fiber-bound polymer fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber made from a polymer of a protein and a vinyl monomer prepared by solubilizing animal hair.

[0002]

2. Description of the Related Art Animal wool fibers such as wool have a unique warm feeling, good heat retention, softness and lightness, not only good hygroscopicity, but also excellent textile and dyeing properties. Although it is very useful as a fiber, it is a natural product, so that only fibers with a limited fineness and fiber length can be obtained, so that the cost is high and its use is restricted.

For this reason, as an alternative to this kind of fiber,
Mainly food proteins, such as milk protein (casein), corn protein, yeast protein, soy protein,
A blend fiber obtained by mixing and spinning peanut protein and gelatin and derivatives of these proteins with viscose.
JP-B-35-2053 and JP-B-36-20765) and fibers obtained by spinning a copolymer of these proteins with a vinyl monomer (for example, JP-B-3-2053).
Nos. 7-18383, 38-9431 and 40-
No. 9059) has been developed and put to practical use.

[0004] However, this type of fiber has the drawback that the protein component containing only about 3 to 40% must be purified at the expense of the valuable food resources.

[0005]

SUMMARY OF THE INVENTION The present invention relates to this technical problem which was not recognized at all in the prior art in the field, that is, the technical problem of utilizing animal hair protein as a regenerated fiber (the reason is as follows). Because animal hair is strongly cross-linked by disulphide bonds, it is very difficult to solubilize it.In addition, if it is dissolved under strong conditions, the degradation of amino acids proceeds, and animal hair proteins cannot be recovered efficiently. To solve the above-mentioned problems.

[0006]

That is, the present invention relates to a polymer comprising an animal hair protein obtained by spinning and drawing a polymer product of a protein prepared by solubilizing animal hair and a vinyl monomer. About fibers.

The animal hair used in the present invention is typically wool, and other examples include, but are not limited to, alpaca, mohair, angora, cashmere, feathers and the like.

[0008] Animal hair is solubilized by an oxidative decomposition method using a relatively high concentration of an oxidizing agent in a weakly alkaline liquid medium, or by using various proteases that hydrolyze keratin, a component of animal hair. Examples thereof include an enzymatic method and a reduction method using mercaptoethanol or mercaptoethylamine, etc., and an oxidative decomposition method is preferable, and this will be described in more detail.

As the liquid medium used in the oxidative decomposition method, water and alcohols (methanol, ethanol, propanol, etc.) are generally used, and these may be used in combination of two or more if desired. Ammonia, alkali metal hydroxides, amines, alkali metal carbonates and the like are exemplified as pH adjusters for the weakly alkaline region of these liquid media, and these are adjusted according to the type of liquid medium or oxidizing agent used. What is necessary is just to select suitably.

Examples of the oxidizing agent include hydrogen peroxide, peracetic acid, formic acid and other peroxides, and are inexpensive, easy to handle, easy to post-process after solubilizing animal hair, and contained in the solubilized material. Hydrogen peroxide is most preferred because no harmful components remain. The concentration of the oxidizing agent is usually at least 20%, preferably 25%.
% To 35%. Animal hair solubilization depends on the type and concentration of the oxidizing agent used and the type of dissolution medium,
The solubilization time is generally about 0.1-1.0 hours. For example, when using treated water whose pH has been adjusted to about 8 using 35% hydrogen peroxide and ammonia, when animal hair is immersed, the temperature naturally rises to about 100 ° C., and solubilization occurs within one hour. Complete, little undissolved material remains. In the case where foreign matter other than animal hair is present, a filtration treatment using a filter of about 100 mesh may be performed.

The method of recovering animal hair as a solid protein from the obtained animal hair solution includes: (i) a method of recovering a gel by adding a volatile inorganic acid, and a method of recovering a volatile protein such as alcohol or acetone. (Ii) a method of precipitating and separating a solubilized animal hair by mixing with an organic acid, and (iii) a method of recovering the solubilized animal hair as a water-insolubilized material by a crosslinking treatment. And the like, but in the present invention, the methods (i) and (ii) are preferred.

By subjecting the solid protein recovered by the above method to a drying treatment, a particle size of about 1 μm to 100 μm is obtained.
An animal hair powder of about μ is obtained.

The vinyl monomer used in the present invention is a vinyl monomer which can be polymerized with the protein obtained by the solubilization treatment of animal hair, and is, for example, acrylonitrile. It is also possible to use acrylonitrile in combination with a plurality of other vinyl monomers. Examples include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylamide, methacrylamide, vinyl acetate, vinyl chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, vinyl sulfonic acid, and allyl sulfonic acid. Acrylonitrile is preferably used in an amount of 70% to 80% of all vinyl monomers in terms of cohesive strength when polymerized.

Examples of a medium for copolymerizing the animal hair protein with a vinyl monomer include an aqueous zinc chloride solution, dimethylformamide, and dimethylacetamide. In view of the solubility of the animal hair protein, zinc salt water is used. Aqueous solutions are preferred. For example, 100 ml of a 60% aqueous solution of zinc chloride
In this case, about 20 g of the wool powder is completely dissolved in a red beige solution.

A vinyl monomer is added to a solution in which animal hair powder is dissolved in the above-mentioned polymerization medium, and a polymerization initiator is further added to polymerize the animal hair protein with the vinyl monomer.

The reaction ratio between the animal hair protein and the vinyl monomer is not particularly limited, but usually the animal hair protein: vinyl monomer = 1: 9 to 5: 5, and the amount of the animal hair protein is too small. In this case, the properties of animal hair fiber cannot be sufficiently imparted to the final fiber product.

As the polymerization initiator, ammonium persulfate,
It is preferred to use a radical polymerization initiator such as potassium persulfate or hydrogen peroxide in an amount of about 0.1 to 5% based on the vinyl monomer, but a redox catalyst such as persulfate-sulfite, chloric acid, etc. -Sulfites or hydrogen peroxide-ferrous salts may be used.

A general polymerization reaction temperature is about 60 to 80 ° C. when a radical polymerization initiator is used, and about 15 to 40 ° C. when a redox catalyst is used.

After the solubilization treatment, the animal hair protein may not be once separated as a powder, but may be subjected to the above polymerization reaction as a solubilized solution. In this case, the polymerization treatment operation is further simplified by solubilizing animal hair in a high-concentration aqueous solution of zinc chloride that can be used as a polymerization medium by the action of an oxidizing agent such as hydrogen peroxide.

By subjecting the polymer prepared by the above polymerization reaction to a spinning step according to a conventional method, a polymer fiber bound to animal hair protein according to the present invention is obtained. In this case, the polymer may be once separated from the reaction mixture and dissolved in a concentrated aqueous solution of zinc chloride to prepare a spinning dope, or the reaction mixture may be directly heated to prepare a spinning dope.

That is, the above-mentioned spinning dope is extruded from a nozzle having an appropriate pore size into an aqueous coagulation liquid maintained at -4 to 25 ° C., for example, an aqueous zinc chloride solution (concentration of about 10 to 40%) to coagulate. The yarn is pre-drawn about 1.1 to 3 times in hot water at about 50 to 80 ° C., and then drawn at a temperature of 100 ° C. or more, for example, about 3 to 7 times in steam, and wound.

[0022]

The present invention will be described below with reference to examples. Example 1 200 g of wool / hemp / polyester = 5/1/4 blended yarn
To the mixture was added 700 ml of treated water adjusted to pH 8 using 35% aqueous hydrogen peroxide and 28% ammonium water, and the mixture was allowed to stand at room temperature. The reaction was violent after 30 minutes, and the reaction was completed 60 minutes after standing. When the reaction mixture was filtered with a 100 mesh filter, hemp and polyester could be almost completely filtered off. Acetic acid was added to the wool solution as a filtrate to lower the pH. The solution was mixed with alcohol and left overnight. Then, the supernatant was discarded, and the wool protein recovered as a precipitate was further washed with alcohol. Finally, it was washed with acetone and air-dried. By this operation, about 70 g of a pale yellow, tasteless and odorless powder was obtained. The amino acid analysis values and IR chart of the obtained powdery protein are shown in Table 1 and FIG. 1, respectively.

[0023]

[Table 1]

A red-brown transparent solution obtained by dissolving 15 g of the above powder in 200 ml of a 37.5% aqueous zinc chloride solution (50 to 60 ° C.) with gentle stirring is added with stirring at a liquid temperature of 1%.
While maintaining at 5 ° C., acrylonitrile 15 ml, 2.5
10 ml of a 37.5% aqueous zinc chloride solution containing sodium sulfite (hereinafter referred to as solution I) and a 37.5% aqueous zinc chloride solution containing 1.5% ammonium persulfate (hereinafter referred to as solution I).
8 ml) was added, and a polymerization reaction was carried out.
After a lapse of 30 minutes, 15 ml of Solution I and 12 ml of Solution II were further added to the reaction solution that turned milky white, and the reaction was continued. After a lapse of 3 hours, a milky white solid precipitated, and the specific odor of acrylonitrile disappeared. The reaction product was left in a thermostat at 60 ° C. for 12 hours to obtain a clear, red brick-colored viscous polymer aqueous solution (viscosity: 144 P).
The polymer was extremely stable, with no change in hue and viscosity over at least 30 days under sealed storage.

The above aqueous polymer solution is extruded into a 20% aqueous zinc chloride solution (15 ° C.) through a spinneret having a hole diameter of 0.1 mm and a number of 25 holes to solidify, and the coagulated yarn is passed through a spinning bath (bath length: 1 m). After being stretched by a factor of four, the polymer was further stretched by a factor of four in steam to obtain a polymer fiber (dry strength: 3.5 g / d or more) combined with wool protein. Table 2 shows the amino acid analysis value and IR chart of the fiber.
And FIG. 2 respectively.

[0026]

[Table 2]

Example 2 32 ml of acrylonitrile was added to a reddish brown transparent solution obtained by dissolving 11 g of the above powder in 200 ml of a 60% aqueous zinc chloride solution with gentle stirring, and then 2.3% of sodium sulfite was added with stirring. 4.0 ml and 3.2 ml of a 60% aqueous solution of zinc chloride containing 60% aqueous zinc chloride and a 60% aqueous solution of zinc chloride containing 1.4% ammonium persulfate, respectively.
One minute later, 8.0 ml and 6.4 ml were added, respectively. Then, stirring was further continued for 1 hour and 30 minutes to obtain a polymer solution. The polymer solution is a viscous solution of red brick color without heating. The polymer solution was spun and stretched in accordance with the procedure of Example 1 to obtain a polymer fiber (3.2 g / d or more) bonded to wool protein.

Example 3 A solution prepared by dissolving 1000 g of zinc chloride in 600 g of water (8
(5 ° C.), 80 g of wool top was immersed, then 50 ml of 35% hydrogen peroxide solution was added, and the wool was dissolved with stirring. After 45 minutes a nearly clear wine-colored solution was obtained. 100 ml of this solution was taken and 15 ml of acrylonitrile was collected.
Was added. Then 35% hydrogen peroxide solution 0.02ml further ferrous sulfate solution _{(0.05g, FeSo 4 7H 2 O} / 5
0.5 ml of 0 ml 60% ZnCl ₂ aqueous solution) was added. The reaction was carried out at 50 ° C. for 5 hours while stirring slowly.
A viscous red brick-colored, transparent reaction solution was obtained in the same manner as in Example 2. Thereafter, the fiber was spun and drawn in accordance with the procedure of Example 1 to obtain a polymer fiber (3 g / d or more) bonded to wool protein.

[0029]

As described above, the polymer fiber conjugated with the animal hair protein according to the present invention has sufficient properties unique to animal hair fiber, and is not only useful as a substitute for animal hair fiber but also natural. Since it is possible to use fibers having a fineness and a fiber length that cannot be obtained with animal hair fibers, it is possible to supply various fiber products according to needs in fields other than those in which conventional natural animal hair fibers are used. Further, according to the present invention, in the animal hair fiber industry, a large amount of fibers generated and discarded when producing clothing from animal hair fibers or fabrics of the animal hairs or the fabrics or the like. Valuable animal hair proteins can be efficiently recovered from debris and trimmings and used effectively as regenerated fibers.

[Brief description of the drawings]

FIG. 1 is an IR chart of a wool protein powder prepared in Example 1.

FIG. 2 is an IR chart of a polymer fiber bonded to wool protein produced in Example 1.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Takashi Chichichi, 303-303 Iwakura-Miyake-cho, Sakyo-ku, Kyoto-shi, Kyoto (72) Fumiaki Sakai 14-5, Shimogita-cho, Neyagawa-shi, Osaka In-house (56) References JP-B-43-9748 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) D01F 4/00 D01F 6/38

Claims (4)

(57) [Claims] 1. A polymer fiber comprising animal hair protein obtained by spinning and drawing a polymer product of a protein and a vinyl monomer prepared by solubilizing animal hair. 2. The fiber according to claim 1, wherein the animal hair is wool. 3. A protein prepared by solubilizing animal hair and a vinyl monomer are polymerized in a polymerization medium, and the obtained polymer product is spun and drawn, and the animal hair protein is bound thereto. A method for producing a polymer fiber. 4. The method according to claim 3, wherein the polymerization medium is an aqueous zinc chloride solution.