JP2001003274A - Animal hair fiber structure having shrink resistance and yellowing resistance, and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a animal hair fiber structure excellent in both shrink resistance and yellowing resistance by pretreating an animal hair fiber structure with a specific anion-type surfactant solution and then treating it with a proteolytic enzyme. SOLUTION: This animal hair fiber structure having yellowing resistance and shrink resistance is obtained by pretreating an animal hair fiber structure made of wool, etc., with an anion-type surfactant solution composed of an aqueous solution where an alkali metal salt of an (un)saturated carbohydrate carboxylic acid of >=8C such as sodium oleate is dissolved in a concentration not smaller than the critical micelle-forming concentration and then treating it with a proteolytic enzyme. The fiber structure also has an X-ray intensity ratio of chlorine atom to sulfur atom which is <=0.5 by fluorescent X-ray spectroscopy, a difference in b* values of perceived chromaticity indexes (CIE 1,976) before and after treatment with steam at 2.5 kg/cm2 for 60 s using a steam press which is <=0.5 and a coefficient of area contraction (IWS TM31 method) which is <5%.

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 excellent in shrinkage resistance (washing resistance) and yellowing resistance and a method for producing the same.

[0002]

Conventionally, animal hair is said to be the most ideal fiber among natural fibers and synthetic fibers due to its excellent moisture absorption / release properties and heat retention properties. Since wrinkles, pilling, felting, and the like are likely to occur and handling is difficult as compared with cotton, synthetic fibers, and the like, various modification processes have been developed.

[0003] Methods of modifying the surface of animal hair to decompose the cuticle of the epidermis of animal hair and the cell membrane complex tissue components in the interstices thereof, as well as the surface portion of the cuticle layer, are referred to as surface modification and descaling. Various processing is performed in combination with or combined with oxidation (chlorine oxidation, oxygen oxidation) processing, reduction processing, enzyme processing, corona discharge processing, plasma processing and the like.

[0004] Specifically, "Dyeing Industry" (Vol.4)
1, p347-363, p566-569, p571-
575, Vol. 42, pp. 133-139), British Patent No. 1150557 (providing shrink resistance by oxidation treatment),
JP-A-55-36324 (oxidation treatment in a concentrated salt solution) and the like are disclosed.

[0005] However, although a method using 100% chemical treatment can provide shrinkage resistance and anti-felting, it has the drawback that the texture of the fibrous structure becomes hard, and the use of a high-concentration salt solution has an adverse effect on the environment. In addition, corona discharge machining and plasma machining are only used in animal hair processing because they harden proteins due to heat and adversely affect the texture. .

[0006] In particular, in the chlorine oxidation processing method using a chlorine compound which is widely used in industry, chlorine reacted and bound to animal hair is separated over time or by steaming or boiling to form a double bond. However, there is a problem that the phenomenon of yellowing animal hair cannot be avoided.

[0007] Therefore, when the workpiece to be chlorine is quantified, it is clearly detected that chlorine is present. In addition, this formulation discharges AOX (Absorbable Organic Halogens) into wastewater, and thus has substantially stopped its industrial role in Western Europe where wastewater regulations are strict.

In the oxygen oxidation or reduction method, AOX
Various methods have been developed with the aim of industrialization, which is expected as a de-AOX method without discharging wastewater. However, these treatments alone have little effect on improving animal hair, and usually require enzymatic treatment or resin processing. There is a need to do. In addition, since the object to be processed by the above method is damaged and whiteness is improved, there is a problem that the degree of yellow change due to the subsequent steaming process is large.

[0009] Furthermore, the resulting reformed result is poor in uniformity and has a strong elongation decrease due to the presence of a site that is strongly damaged, and thus has a large adverse effect on spinnability and physical properties of spun yarn. Because the degree of modification obtained is low for that,
Until now, there have been few examples of success in industrial application to animal hair slivers.
The use of a special oxidation method, as disclosed in JP-A No. 2000-125, etc., is only slightly known. For this reason, there has been a demand for the development of a new shrink-proof processing method which does not discharge AOX, is uniform and has little damage to animal hair.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and does not use chlorine or an oxidizing / reducing agent in a manufacturing process, has little damage to animal hair, has excellent shrinkage resistance, and has excellent shrinkage resistance. It is an object of the present invention to provide a washable animal hair fiber structure and a method for producing the same.

[0011]

The present invention has the following configuration to achieve the above object.

The first invention is that b ^{* in} the CIE1976 (L ^* , a ^* , b ^* ) perceived chromaticity index before and after passing steam of 2.5 kg / cm ² for 60 seconds with a steam press machine ^. Value difference Δb ^* is 0.5 or less and I
An animal hair fiber structure having an area shrinkage ratio of less than 5% according to the WS.TM31 method. The second invention is directed to the first invention, wherein the fluorescence of chlorine atoms with respect to sulfur atoms in the first invention is The X-ray intensity ratio is 0.5% or less.

[0013] Next, a third invention is a method for producing the above-mentioned shrink-proof animal hair fiber structure, wherein the alkali metal salt of a saturated or unsaturated carbohydrate carboxylate having 8 or more carbon atoms has a concentration of not less than the critical micelle forming concentration. After pre-treating the animal hair fiber structure with an anionic surfactant composed of an aqueous solution, the fiber structure is treated with a protease. A method for producing an animal hair fiber structure.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a second method will be described. In the present invention, animal hair fibers mainly refer to wool, but are not limited thereto, and may include cashmere,
Mohair, alpaca, camels, rabbits and the like can also be used.

In the method of the present invention, a pretreatment with a surfactant is performed, followed by a treatment with a protease. The surfactant belongs to an anionic surfactant and has 8 carbon atoms. It is important to use the above saturated or unsaturated carbohydrate carboxylic acid alkali metal salts.

At this time, it is necessary to deposit and adsorb the aggregate micelles of the surfactant on the surface of the animal hair. For this purpose, (a) use a high-concentration surfactant, and (b) use a liquid temperature. Is effective to reduce the solubility of micelles at a high temperature. However, drying may be performed after the surfactant treatment, and if necessary, the adhesion amount may be confirmed.

Table 1 below shows various concentrations (g / l) of sodium oleate in the surfactant and the amount of the surfactant attached per unit weight of wool (undyed and dyed) (weight). %). FIG. 1 shows the relationship between the amount of surfactant attached and the weight loss rate when pretreatment was carried out using the above-mentioned surfactant and subsequently enzymatic treatment (biopulase treatment), and FIG. 2 shows various carbon numbers. 1 shows the relationship between the amount of surfactant attached to wool and the rate of weight loss by enzymatic processing.

[0018]

[Table 1]

Thus, it can be seen that the use of a surfactant having a concentration of sodium oleate equal to or higher than the critical micelle formation concentration (0.25 g / l) is effective for reducing animal hair, that is, for decomposing animal hair with enzymes.

The above-mentioned “saturated or unsaturated carbohydrate carboxylate alkali metal salt” has insufficient hydrophobicity if it has less than 8 carbon atoms, and is therefore drawn into water and localized on the animal hair surface. It is necessary for the number of carbon atoms to be 8 or more because of low efficacy. When the number of carbon atoms is 10 or more, more optimal deposition and adsorption can be performed.

The above-mentioned alkali metal carboxylate is pretreated with an aqueous solution having a concentration equal to or higher than the critical micelle formation concentration and adhered to the animal hair surface, and then treated with a protease to obtain a uniform modification effect. The reason has not been disclosed.

However, since the carbon chain of the surfactant is hydrophobic, it adheres to the hydrophobic scale surface and the hydrophilic portion (carboxylic acid terminal group) of the terminal group of the surfactant faces water. Since the entire surface of the scale will be hydrophilic, during subsequent enzymatic processing, the enzyme will suffer from extreme uneven adhesion and extreme degradation damage to the hydrophilic part from the scale gap of animal hair to the cell membrane complex tissue component. Curb,
The animal hair protein degradation phenomenon by the enzyme proceeds simultaneously in the area larger than both sides of the outer surface of the scale (epicicle, exocicle) via the scale surface and the gap between the scales. It is considered that the effect is also made uniform.

After the treatment with such a surfactant,
Subsequently, treatment with proteolytic enzymes is performed,
The protease used in the present invention is a neutral protease,
Any of acidic protease and alkaline protease can be used.

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

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 significantly impair the enzyme activity.

For example, in the pH range of 7.5 to 9.5, a buffer solution of sodium carbonate-sodium bicarbonate, phosphoric acid-sodium phosphate, trishydroxyaminomethane-hydrochloric acid, boric acid-sodium borate and the like may be used. it can.

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 in consideration of waste liquid treatment, and usually in the range of 10 mM to 100 mM. Set to.

The temperature of the enzyme treatment varies depending on the type of the enzyme. The higher the temperature, the better the stability of the enzyme is not significantly reduced.
Is set in the range.

After the enzyme processing, the activity of the enzyme is stopped.
Deactivate. 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.

By using the above manufacturing method, the first shrink-proof animal hair fiber structure can be obtained.

Hereinafter, description will be made based on embodiments.

(Example 1) After weaving a pure wool fabric with a basis weight of 300 g / m ² by twill weaving using a twin yarn of 60th count (meter count) in both directions, the fabric was put into a jet dyeing machine, At a ratio of 1:30, sodium stearate (carbon number: 18,
A 5.0 g / l aqueous solution (critical micelle formation concentration: 0.24 g / l) was used as a surfactant and treated at 90 ° C for 15 minutes.

After the surfactant was drained and the woven fabric was dried, the amount of the surfactant applied to the woven fabric was measured and found to be 6.1% by weight. Subsequently, 0.05% of a 50 mM phosphate buffer (pH 8.2) was added, the temperature was raised to 50 ° C., and 0.5 to 5.0 g / l using Savinase (Alkaline protease manufactured by Novo Nordisk). Bath ratio 1: 3
The mixture was treated at 50 ° C. for 60 minutes at 0 ° C., and then the pH was lowered to 4 or less by adding formic acid to inactivate the mixture, and the processing was stopped.

[0034] The woven fabric obtained in this way is
When the area shrinkage was measured according to the TM31 method (after 5 A cycles × 3 times), the area shrinkage was 0.5% at the minimum part and 3.0% at the maximum part. It turned out to be a certain dough. Further, the woven fabric is subjected to a Hoffman press at a vapor pressure of 2.5 kg / cm ² for 60 hours.
The yellowing degree Δb ^* in the case of the second steaming was 0.2, and it was found that there was almost no discoloration.

(Comparative Example 1) A twill woven pure wool woven fabric having a basis weight of 300 g / m ² , woven using a 60-count double yarn (metric count) in both courses, was charged into a jet dyeing machine (Swing Ace, Nissen). The mixture was treated at 90 ° C. for 15 minutes with a 0.15 g / l aqueous solution having a bath ratio of 1:30 and a concentration lower than the critical micelle formation concentration of sodium stearate (0.24 g / l).

After the waste solution, a 50 mM phosphate buffer (pH
8.2) Add 0.05% and raise the temperature to 50 ° C.
5.0 g / l of savinase (Alkaline protease manufactured by Novo Nordisk) was added and the mixture was treated at 50 ° C. for 2 hours. Then, the pH was lowered to 4 or less by adding formic acid, and the processing was stopped.

The degree of yellowing Δb ^* of the woven fabric thus obtained was measured by the same method as in Example 1. As a result, it was 0.2 and almost no yellowing was observed. As a result of measuring the area shrinkage, the area shrinkage was as large as 14%, and the fluff was large.

The physical properties of Example 1 and Comparative Example 1 are shown below.

[0039]

[Table 2]

Example 2 An animal hair sliver (25 g / m) having an average single fiber diameter of 21.5 μm was added to sodium palmitate (carbon number: 16; critical micelle forming concentration: 0.85 g / m).
After padding to 50 g / l of the aqueous solution of 1), the substrate is further immersed in an aqueous solution of the same formulation at 80 ° C. for 1 minute and padded.

Thereafter, 5 g / l of Alcalase was added to 50 mM
It was immersed and padded in a 30 ° C. solution in a borate buffer (pH 8.5) for 30 seconds, and further added to a solution of the same formulation at 60 ° C.
The step of dipping and padding for 0 seconds was repeated five times. Then, it is immersed in a 1 g / l solution of formic acid and padded, and then at 40 ° C.
Immersed in hot water and allowed to dry, and then dried.

Using the sliver obtained by the above treatment, a twisted 280 T / m and a twisted 480 T / m 48-count double yarn (meter-count) is spun, and the spun yarn has a cover factor of 0.41 in India. After knitting the knitted fabric, IWS
-The area shrinkage rate after 5 times of 5A cycles was measured by the TM31 method.

As a result, the area shrinkage was 3.5%, there was little fuzzing, the water washability was excellent, and the yellowing degree Δb ^* by the same steaming treatment as in Example 1 was 0.3.
Thus, a yarn which hardly yellowed was obtained.

Comparative Example 2 0.1 g / l of a dialkyl sulfosuccinate penetrating / wetting agent, 5 g / l of alcalase, 50 mM boric acid were added to animal hair sliver (25 g / m) having an average single fiber diameter of 21.5 μm. The process of immersing in a 60 ° C. solution in a buffer solution (pH 8.5) for 30 seconds × pad was repeated six times, then immersed in formic acid 1 g / l, immersed and padded in 40 ° C. warm water, and then dried.

Using the sliver thus treated, a twisted 280 T / m and a twisted 480 T / m 48-count twin yarn (metric count) is spun, and the cover factor is set to 0.1.
41 knitted fabrics of India were knitted. The knitted fabric is
As a result of measuring the area shrinkage rate based on the TM31 method, the area shrinkage rate was 67%, the felting was remarkable, and the water washability was poor.

(Comparative Example 3) An animal hair sliver (25 g / m) having an average single fiber diameter of 21.5 μm was put into a dialkyl sulfosuccinate-based osmotic / wetting agent of 0.1 g / l and available chlorine of 0.2 g / l. After being immersed in the solution at room temperature for 30 seconds and padding, water washing is performed for 30 seconds, the pad is treated with acidic sulfurous acid for 30 seconds, the pad is washed with warm water for 30 seconds, the pad is washed with water for 30 seconds, and the pad is dried after passing through the respective steps.

Using the sliver thus treated, a twisted 280 T / m and a twisted 480 T / m 48-count twin yarn (metric count) is spun, and the cover factor is set to 0.1.
41 knitted fabrics of India were knitted. The knitted fabric is
The area shrinkage was measured by the same method as in Example 1 based on the TM31 method. As a result, the area shrinkage was 2.3%, which was excellent in water-resistant washing property. As a result of measurement of Δb ^* , the yellowing degree was as large as 1.2.

The physical properties of Example 2 and Comparative Examples 2 and 3 are shown below.

[0049]

[Table 3]

Example 3 First Twist 280 T / m, Lower Twist 48
The knitted yarn of 48 T (m count) of 0 T / m was packaged, treated with sodium oleate at 5 g / l and a bath ratio of 1:15 at 90 ° C. for 20 minutes by a package dyeing machine, and then drained.・ Protease N5% owf, pH
Treated at 7.0 at 50 ° C. for 30 minutes.

After the waste liquid, dyeing was carried out using an acid dye according to a conventional method. Then, a knitted fabric having a cover factor of 0.41 was knitted, and the area shrinkage after 5 times of 5 cycles of IWS / TM31 method was measured. The shrinkage was 4.8%, the degree of yellowing was small, and a dyed yarn having washability with water was obtained.

(Comparative Example 4) Twisting 280 T / m, priming 48
A knitted yarn of a 48-count double yarn (meter-count) of 0 T / m is packaged, and a 0.1 g / l sodium oleate solution having a critical micelle forming concentration (0.25 g / l) or less is used in a package dyeing machine, 90 ° C × 2 at a bath ratio of 1:15
After treating for 0 minutes, the solution is drained and 5% of enzyme / protease N is added.
Using owf, treatment was performed at 50 ° C. for 30 minutes at pH 7.0.

After the waste liquid, dyeing with an acid dye is carried out according to a conventional method, and then a knitted fabric is knitted with a cover factor of 0.41, and the area shrinkage is measured by the IWSTM31 method.
The area shrinkage was 50%, the upper felt was remarkably formed, and the dyed yarn had poor water-washing resistance.

The physical properties of Example 3 and Comparative Example 4 are shown below.

[0055]

[Table 4]

As a result, the products of Examples 1 to 3 and Comparative Example 3 had an area shrinkage of 5% or less.
Products 2 and 4 had extremely large area shrinkage. The products of Examples 1 to 3 and Comparative Examples 1, 2 and 4 all had a yellowing degree (Δb ^* ) of 0.5 or less, but Δb ^{* of} Comparative Example 3 was 1.2 or more. It was larger than the example. Thus, Examples 1 to 5 obtained by the method of the present invention
The cloth No. 3 was found to be excellent in both shrink resistance and yellowing resistance.

Further, since the products of Examples 1 to 3 did not use any chlorine compound, the fluorescent X-ray intensity ratio of chlorine atoms to sulfur atoms was measured by X-ray fluorescence analysis. 1 = 0.09 to 0.24
%, Example 2 = 0.32%, Example 3 = 0.12%,
Although almost not detected, the product of Comparative Example 3 treated with chlorine had the fluorescent X-ray intensity ratio of 1.22%.

[0058]

The animal hair fiber structure obtained according to the present invention has little yellowing due to the steaming step or dyeing, has excellent whiteness, and has excellent shrink resistance, so that it can be washed at home. It works.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the amount of surfactant attached and the wool weight loss rate.

FIG. 2 is a graph showing the relationship between the number of carbon atoms of an alkali metal carboxylate in a surfactant used for pretreatment, the amount of surfactant attached, and the rate of wool weight loss due to enzyme processing.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Michinobu Kamori, 1-2-2 Umeda, Kita-ku, Osaka-shi, Osaka Kanebo Textile Co., Ltd. (72) Tatsuya Sugimoto 1 Umeda, Kita-ku, Osaka, Osaka C-2-2 Kanebo Textile Co., Ltd. F-term (reference) 4L031 AA05 AB01 BA32 BA33 BA39 CA06 DA00 DA20

Claims (3)

[Claims] 1. A steam press machine with 2.5 kg / cm ²
CIE 1976 (L) before and after passing steam for 60 seconds
^* , A ^* , b ^* ) Difference in b ^* value in perceived chromaticity index Δb ^*
Is less than or equal to 0.5 and the area shrinkage ratio in the IWSTM31 method is less than 5%. 2. The X-ray fluorescence intensity ratio of chlorine atoms to sulfur atoms in the fluorescent X-ray analysis method, that is, the X-ray intensity of sulfur atoms (kcps) is converted to the X-ray intensity of chlorine atoms (kcp).
The animal hair fiber structure according to claim 1, wherein a value obtained by dividing by s) and multiplying by 100 is 0.5% or less. 3. An animal hair fiber structure is prepared by using an anionic surfactant comprising an aqueous solution having a concentration of a saturated or unsaturated carbohydrate carboxylate alkali metal salt having 8 or more carbon atoms at a concentration higher than the critical micelle forming concentration. A method for producing an animal hair fiber structure having shrinkage resistance and yellowing resistance, comprising treating the fiber structure with a proteolytic enzyme after the treatment.