JPH1060780A - Animal hair fibrous structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate a prickling feeling peculiar to an animal hair fiber and obtain an animal hair fibrous structure, having a refreshing feeling and washable at home by spinning and weaving a partially oxidized animal hair fiber or forming an animal hair fiber structure, further partially oxidizing the formed fiber structure and treating the partially oxidized fiber structure with a proteolytic enzyme. SOLUTION: An animal hair fiber such as wool is treated by partial oxidation with a hypochlorite and then spun and woven or a wool woven fabric is treated by the partial oxidation and then enzymically treated with a proteolytic enzyme such as an alkaline protease, produced by an alkalophilic species of the genus Bacillus and having keratin hydrolytic properties, a protease derived from Bacillus lentus or an alkaline protease produced by a microorganism into which a gene thereof is transduced to provide >=5 and <=30% weight reduction ratio.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an animal hair fiber structure which has no tingling sensation which is peculiar to animal hair, has a refreshing sensation and washing resistance and can be washed at home.

[0002]

2. Description of the Related Art Animal hair is said to be the most ideal fiber among natural fibers and synthetic fibers due to its excellent moisture absorption / desorption properties and heat retention. On the other hand, animal hair is liable to be shrunk, wrinkled, pilled, or felted by washing, and is difficult to handle as compared with cotton, synthetic fiber, and the like. In addition, the tingling sensation peculiar to animal hair fiber, innerwear that directly touches the skin,
It has prevented the development of casual shirts for spring and summer.

In order to expand the uses of animal hair fibers, washing resistance and reduction of tingling are essential requirements, and some reports have been made. For example, there is an oxidation treatment for chemically removing cuticles on the surface of animal hair as shrink-proofing and anti-felting treatment of animal hair fiber structure (UK Patent No. 1150).
557). Furthermore, a method has been proposed in which the oxidation treatment is carried out in a concentrated salt solution so that the fiber is not unnecessarily reduced in strength (JP-A-55-36324).
The chemical treatment method has a drawback that the texture of the animal hair fiber structure becomes hard in exchange for shrink resistance and anti-felting.

[0004] There is an enzyme treatment as a method of modifying animal hair without chemical treatment. In this method, animal hair, animal hair fiber, or animal hair fiber structure is mainly treated with a protease to modify texture, improve dyeability, and impart shrinkage resistance. In general, it is considered that a weight reduction of about 1 to 3% is sufficient to improve the dyeing property, but further weight reduction is required to modify the texture and impart shrinkage resistance. However, weight loss by protease treatment alone is accompanied by a significant decrease in strength. This is because the cuticle on the surface is chemically stable and is not easily decomposed by enzymes, whereas the hydrophilic layer (C) is relatively easily decomposed.
It is considered that the MC layer and the cortex layer swell in water, and the protease preferentially degrades the hydrophilic layer.

Hitherto, several methods have been proposed for controlling the swelling of the hydrophilic layer to control the permeation and action of the protease into the hydrophilic layer. For example, (1)
A method in which an enzyme reaction is carried out in a nearly saturated inorganic salt solution (Japanese Patent Publication No. 1-54471, Japanese Patent Publication No. 57-53470), and (2) A method in which an animal aqueous solution is emulsified and dispersed in an organic solvent to treat animal hair 51-3, 1899), and (3) a method using a protease which is active in a neutral to weakly acidic region where the degree of swelling of the hydrophilic layer is relatively small (JP-A-4-174778). However, in (1) and (2), the treatment of a high-concentration salt solution or an organic solvent waste solution is a problem. As shown in (3), the titer of neutral and acidic proteases is generally lower than that of alkaline protease, and sufficient processing is required. A large amount of enzyme is required to achieve the effect. In addition, these enzyme treatments are not suitable for summer because swelling occurs even if a shrink-proof material is obtained.

[0006] As a method for compensating for the disadvantages of the chemical treatment and the enzyme treatment, a method of using both together has also been proposed.
For example, as a method for completely removing scale, there is a method of subjecting animal hair to oxidation treatment, washing with water, reduction, and then protease treatment (Japanese Patent Application Laid-Open No. 1-54471). Protease treatment is carried out in a highly concentrated salt solution. However, there is a problem in treating high-concentration salt effluent.

[0007] Further, any animal hair fiber structure using the above-described scale-removed animal hair fibers has a tingling sensation peculiar to animal hair, and is unsuitable for uses such as innerwear and casual shirts for spring and summer. is there.

[0008]

DISCLOSURE OF THE INVENTION In view of the above-mentioned circumstances, the present inventors do not have the tingling sensation peculiar to animal hair, have shrink-proof properties,
As a result of intensive studies to obtain an animal hair fiber structure that can be washed at home, the present invention has been completed. SUMMARY OF THE INVENTION An object of the present invention is to provide a washable material having both excellent texture (elimination of tingling and refreshing feeling) and washing resistance.

[0009]

SUMMARY OF THE INVENTION The above-mentioned object is achieved by spinning partially oxidized animal hair fibers to form an animal hair fiber structure, or after partially oxidizing animal hair fiber yarn to form a woven fabric, Alternatively, it is achieved by partially oxidizing the animal hair fiber structure and then treating it with an alkaline protease having keratinolytic activity in a dilute buffer.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Animal hair fibers used in the present invention mainly refer to wool, but are not limited thereto.
Cashmere, mohair, alpaca, camels, rabbits and the like can also be used.

The oxidizing agent is not particularly limited, and various oxidizing agents such as hypochlorite, chlorite, dichloroisocyanurate, permanganate, hydrogen peroxide, monopersulfuric acid and salts thereof can be used. Oxidizing agents can be used, but hypochlorite, dichloroisocyanurate, and permanganate are preferably used.

The purpose of the oxidation treatment is to promote the enzymatic processing of the scale by damaging the scale surface, but not to completely remove the scale. That is, the oxidation treatment should be stopped to such an extent that the scale is not completely removed. The standard is that the area felt shrinkage in the washing test according to the IWS test method TM31 (weskater method) is 80% of that before the oxidation treatment.
Or less, preferably 30% or less.

The protease used in the present invention is an alkaline protease having a greater processing effect than neutral protease and acidic protease. As alkaline protease, bioprase conc (manufactured by Nagase Seikagaku),
Entilon SAL (Rakuto Kasei), Esperase, Alcalase, Savinase (Novo Nordisk) and the like are mentioned. To suppress the strong decrease in animal hair fiber structure due to weight loss due to enzyme processing, the Anson titer It is better to use an enzyme having a high keratin-degrading activity, and even if the protease is derived from the same Bacillus subtilis, a protease produced by Bacillus subutilis or Bacillus lichemiformis (for example, Alcalase; Novo. Bacillus lentus produced by Bacillus lentus, such as sabinase and esperase (both from Novo Nordisk), are more suitable than Nordisk.

Bacillus cereus
In some cases, animal hair fibers were processed using a high keratin-degrading protease derived from the animal (Japanese Patent Application Laid-Open No. 8-89243), but the treatment was uneven (descaling rate = 2 to 3 fibers / 10 fibers) and the enzyme keratin was used. High selectivity but low titer requires large amounts of enzyme and processing time. In addition, Japanese Patent Application Laid-Open No. 8-89243 describes
The rate of weight loss by the enzyme processing disclosed in Japanese Patent Application Laid-Open No. H10-205163 is as low as 5% or less, and although it has a shrinkproof effect, a remarkable change in texture cannot be expected.

The pH at which the enzyme is processed can be selected in accordance with the characteristics of the enzyme and the swelling characteristics of the animal hair fibers used. For example, when wool is processed using an alkaline protease derived from Bacillus subtilis, the enzyme has high potency and stability,
It is preferable to carry out at pH 7.5 to 9.5, which causes less damage to wool.

As the buffer salt to be used, any buffer salt can be used as long as it has a buffering capacity in the pH range for processing and does not greatly impair the enzyme activity. For example, in the pH range of 7.5 to 9.5, a buffer solution of sodium carbonate-sodium hydrogen carbonate, phosphoric acid-sodium phosphate, trishydroxyaminomethane-hydrochloric acid, boric acid-sodium borate, or the like can be used.

The concentration of the buffer salt is not particularly limited. However, since there is almost no change in pH due to the enzyme reaction, the concentration is preferably 500 mM or less for waste liquid treatment, and usually 10 mM or less.
Set in the range of １００100 mM.

As the penetrant, any penetrant that does not inhibit the enzyme and does not significantly impair the stability can be used. Most penetrants and refining agents used for dyeing of animal hair fiber structures can be used. However, nonionic surfactants such as polyoxyethylene alkyl ethers and sucrose esters are particularly preferred.

The temperature of the enzyme treatment varies depending on the type of the enzyme, but it is preferably as high as possible unless the stability of the enzyme is significantly reduced, and is usually set in the range of room temperature to 80 ° C., preferably 30 ° C. to 60 ° C.

Normally, the weight loss rate when removing scale and imparting shrinkage resistance by chlorine processing or the like does not exceed 5%, but the object of the present invention is to eliminate the tingling sensation and modify the texture. is there. The rate of weight loss by enzymatic processing in the method of the present invention is 5% to 30%, preferably 10% to 20%.

After the enzyme processing, the activity of the enzyme is stopped and deactivated. Usually, alkaline protease shows almost no activity at pH 6 or lower and has very low stability. Therefore, when acidified, the activity of the alkaline protease is quickly stopped, and it is not necessary to deactivate it again. Deactivate.

(Reagents used for measuring Anson titer) When a commercially available enzyme preparation was measured by the activity measuring method described in the following section,
The enzyme solution was diluted with water so that the absorbance difference was 0.5 to 1. Milk casein (manufactured by Wako Pure Chemical Industries, Ltd.) was dried at 105 ° C. for 2 hours, 3 g of the casein was accurately weighed, dispersed in 400 ml of a 50 mM disodium hydrogen phosphate solution, and dissolved in boiling water.
Heat and dissolve for 5 minutes. After cooling to room temperature, the pH was adjusted to 8 with an N / 10 sodium hydroxide solution, and 500 ml of water was used as a substrate solution. A stop solution was prepared by making 18 g of trichloroacetic acid, 18 g of anhydrous sodium acetate, and 55 ml of 6N acetic acid to 1 liter with water. A commercially available phenol reagent (2N hydrochloric acid solution: manufactured by Wako Pure Chemical Industries, Ltd.) was diluted twice with water to obtain a color developing solution.

(Method of measuring Anson titer) 1 ml of the enzyme solution is added to a test tube, and the mixture is preheated in a constant temperature water bath at 37 ° C for 5 minutes. Add 5 ml of the substrate solution also preheated to 37 ° C.
Incubate at 37 ° C for 10 minutes. After adding 5 ml of the stop solution and shaking well, the mixture was allowed to stand at room temperature for 30 minutes or more, and then filtered (Toyo Filter Paper No. 131) or centrifuged.
The precipitate is removed, and 1 ml of the filtrate (or supernatant) is collected in another test tube. To this, 2.5 ml of a 0.55 M sodium carbonate solution and 0.5 ml of a coloring solution are added, and the color is developed in a constant temperature water bath at 30 ° C. Then, after 30 minutes, the absorbance at 660 nm is measured. After adding a stop solution before adding the substrate to the enzyme solution, the same process is performed on the solution added with the substrate solution,
The absorbance at 660 nm is measured and used as a blank.
The titer of the enzyme solution is obtained by the following equation (1). Titer (unit / ml) = (absorbance difference from blank) × 58 × 1.1 (1)

(Reagents used for comparison of keratinase titer) Wool powder (manufactured by Nakarai Chemical) is sieved,
5 g of 100 mesh or less was degreased by shaking at 70 ° C. for 4 hours in 500 ml of a 50% aqueous n-propanol solution, filtered, washed and dried to obtain a substrate. As the buffer, a 0.1 M sodium phosphate buffer (pH 8) was used. 0.2% to improve the wettability of wool powder
An aqueous solution of octylphenyl ether of polyoxyethylene (pH 10) was used as the permeate. The undiluted solution of the enzyme solution was diluted to about 4750 units / ml based on the measurement result of Anson titer.

(Comparison method of keratinase titer) 1 ml of a permeate and 2 ml of a 0.1 M phosphate buffer (pH 8) are added to 100 ml of wool powder as a substrate, followed by stirring and dispersion. To this, 1 ml of the enzyme solution was added, and 37 ° C, 0, 20, 40,
After reacting for 60 minutes, 4 ml of the stop solution used for the Anson titer measurement is added to stop the reaction. After the reaction is stopped, the solid content is removed by centrifugation, and the supernatant is operated according to the method of quantifying a protein by Lowry et al., And the absorbance at 660 nm is measured. The difference from the absorbance at reaction time 0 was plotted against the time axis, and the keratin-decomposing activities were compared.

The results of comparison of the Anson titer and the keratinase titer of the three alkaline proteases from Novo Nordisk are shown in Table 1 and FIG.

[0027]

[Table 1]

[0028]

FIG.

[0029]

Example 1 A woven fabric using wool partially chlorinated (area shrinkage ratio of 30% with respect to a woven fabric not chlorinated by the IWS TM31 method) and a woven fabric using plain yarn not chlorinated , 50 mM phosphate buffer (pH 8.2)
Medium, Sabinase 16.0L (Novo Nordisk)
Table 2 and FIGS. 2 to 4 show the results of treatment at 50 ° C. with 2.5% owf and a bath ratio of 1:40.

[0030]

[Table 2]

[0031]

FIG. 2

[0032]

FIG. 3

[0033]

FIG. 4

As shown in FIG. 2, the weight of the partially chlorinated woven fabric was reduced in a short time, and it was recognized that the enzyme processing was accelerated by the partial chlorination. The strength reduction at the same weight loss rate was smaller for the partially chlorinated woven fabric (FIG. 3), and the strength reduction was 20% at a weight loss rate of 10% and the practical strength was sufficient even at 15%. Depending on the use of the original fabric, even if the weight loss rate is 20%, it has practical strength. In addition, there is almost no swelling due to processing that is common in enzyme processing (FIG. 4), and the material is thin and has a cool feeling.

[0035]

Example 2 Using the same woven fabric as in Example 1, Alcalase, Sabinase and Esperase (manufactured by Novo Nordisk) in 50 mM borate buffer (pH 8.5) at 50 ° C.
Table 3 shows the results of the processing.

[0036]

[Table 3]

When the Anson titers are the same, the weight is reduced more by using an enzyme having a higher keratin-degrading activity, and the weight loss rate is higher with the partially chlorinated yarn. Particularly, an enzyme having a high keratin-decomposing activity per Anson titer is preferable, and esperase and sabinase (both from Bacillus lentus) are more suitable than alcalase (from Bacillus licheniformis).

[0038]

Example 3 Partial chlorine processing (the area felt shrinkage rate by IWS TM31 method was 2
0%) wool fabric (60 double threads, twill weave,
300m) and 10m were applied to a jet dyeing machine (Swing Ace, Nissen), and a 50 mM phosphate buffer (pH 8.2) and a penetrant (ES-
100N; Nissei Chemical Co., Ltd.) was added to the solution at 0.05%, the temperature was raised to 50 ° C., and savinase 1 equivalent to 2.5% owf was added.
6.0 L was added, the mixture was processed at 50 ° C. for 2 hours, and the pH was lowered to 4 or less by adding formic acid, and the processing was stopped. After washing with water, dyeing was continued with an acid dye, followed by a normal finishing.

As shown in Table 4, the obtained woven fabric has no tingling sensation as compared with the original fabric, has a soft and refreshing texture, and has greatly improved washing resistance.
It had sufficient performance as a washable material for spring and summer casual shirts.

[0040]

[Table 4]

[0041]

The animal hair fiber structure obtained by the method of the present invention has a sufficient practical strength even at a weight loss rate of more than 10%, has no tingling sensation peculiar to animal hair, and has a refreshing feeling and luster. In addition, it has excellent performance that it is shrinkproof and can be washed at home. These materials are suitable as materials for innerwear, casual shirts for spring and summer, and the like.

[Brief description of the drawings]

FIG. 1 is a graph showing a comparison of keratin degradation activity per Anson titer.

FIG. 2 is a view showing a difference between yarns in a relationship between an enzyme treatment time and a weight loss rate.

FIG. 3 is a diagram showing a difference between yarns in a relationship between a weight loss rate and a decrease in strength.

FIG. 4 is a diagram illustrating a difference between yarns in a relationship between a weight loss rate and a compression characteristic (LC).

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Takamitsu Kashiwamura, Inventor 6-14A-315, Sekime, Joto-ku, Osaka-shi, Osaka (72) Michinobu Kaimori 1-2-2, Umeda, Kita-ku, Osaka-shi, Osaka issue

Claims (4)

[Claims] 1. An animal hair fiber structure obtained by spinning partially oxidized animal hair fibers or partially oxidizing an animal hair fiber structure and then treating with a protease. 2. The animal hair fiber structure according to claim 1, wherein the weight loss rate by the protease is 5% or more and 30% or less. 3. Bacillus (Baci) for proteolytic enzyme treatment.
The animal hair fiber structure according to claim 1 or 2, wherein an alkali protease which is produced by an alkaliphilic bacterium belonging to the genus llus and has keratin-degrading activity is used. 4. The method according to claim 1, wherein a protease produced by Bacillus lentus or an alkaline protease produced by a microorganism into which the gene has been introduced is used for the protease treatment. Animal hair fiber structure.