JPH02216263A - Epoxidation treatment of animal fiber material - Google Patents

Abstract

PURPOSE: To provide an animal fiber material with shrink resistance without impairing essential characteristics of the fiber by subjecting the animal fiber material to a wetting-deswelling treatment with a saturated aqueous solution containing a neutral salt, then adding a reducing agent to the solution, carrying out a reduction treatment and performing cross-linking and polymerization by a treating solution containing an epoxy compound. CONSTITUTION: An animal fiber material is subjected to a wetting-deswelling treatment with a saturated aqueous solution containing preferably sodium chloride at 30-50 deg.C and then a reducing agent (e.g. acidic sodium sulfite) is added to the solution. The animal fiber material is reduced with the solution at 30-50 deg.C and 1-5% wt/v of an epoxy compound (preferable example glycerol glycidyl ether) and an acidic sulfite as a catalyst are added to the solution to give a treating solution. The animal fiber is treated with the treating solution to perform a cross-linking treatment between scales. An elevation of scales in water controlled to prevent felt formation of the fiber. Neither damage of water repellence of skin being essential characteristics of the fiber nor reduction in mechanical strength of the fiber are brought about by the treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for epoxidizing animal fiber materials. More specifically, the present invention provides for materials containing animal fibers having scales in the epidermal tissue.
Concerning an epoxidation treatment method that protects the epidermal tissue and imparts shrink-proofing properties without reducing its saline properties or mechanical strength [Conventional technology] In general, there are various reasons why animal fibers become felted. Although it is not simple as it includes the factors of It is well known that the anisotropy of the friction coefficient is a major factor.

In other words, the larger the difference between the friction coefficient μm of the animal fiber in the direction toward the hair tip and the friction coefficient μ2 in the direction toward the hair root, the easier the animal fiber is to be felted. For this reason, in the shrink-proofing process for animal fibers, it is generally difficult to make the above-mentioned μm and μ2 equal.

In general, the degree of shrink-proofing is expressed by the anisotropy of the friction coefficient (D, , F, , E) defined as below.

Another principle method for shrink-proofing animal fiber materials is to produce products with all the fibers aligned in the same direction (hair root → hair tip), like sheaveskin. It is known that the products produced by this method do not become felted. However, in animal fiber materials, the fiber direction becomes random during the spinning process, for example, so it is extremely difficult to implement the above method.

Therefore, at present, for shrink-proofing of animal fiber materials,
A practical method is to eliminate the anisotropy of the friction coefficient on the fiber surface. As such shrink prevention methods, those listed in Table 1 are known.

Table 1 below is a margin.Various anti-shrink treatment methods for animal fibers 2) Descaling Vantean processing (chlorine treatment in the presence of metal salts) Enzyme treatment In Table 1, the above-mentioned resin coating method (1) has the following problems. Generally, the surface of animal fibers is hydrophobic, indicating the water-repellent function of this fiber, and for this reason, it is very difficult to coat this hydrophobic fiber surface with a hydrophilic polymer. Therefore, a method is known in which the surface of animal fibers is made hydrophilic by treatment with an aqueous solution of an organic or inorganic chlorine agent, and then treated with cationic polyamide shrimp chlorohydrin. According to this method, the product obtained has good shrink-proofing properties, but the water repellency inherent in animal fibers is reduced, and the chemical agents used, such as chlorine agents and dechlorinating agents consisting of sulfites, are
A hydrophilic non-keratin protein that penetrates into the interior of animal fibers, causes a chemical reaction there, and as a result joins animal fiber tissue cells. ) is eluted, reducing the bonding force of Mi weaving of animal fibers, and as a result, the mechanical strength of animal fibers decreases.

-F descaling method (2) has the following problems. That is, since the scale of the animal fibers is removed, the resulting product has good shrink-proofing properties, but it is necessary to avoid a decrease in water repellency and a decrease in the mechanical strength of the fibers as in the case of method 1) above. I can't.

The scale tip removal method (3) has the following problems. That is, since the tips of the scales of animal fibers are removed, the anti-shrinkage effect is naturally lower than in methods 1) and 2) above, but if chemical treatment is applied, the water-repellent function of the fibers will be reduced. At the same time, the mechanical strength of the fibers also decreases. Furthermore, when discharge treatment is included, the water repellent function of the fibers is reduced.

The method (4) for removing cell membrane complexes between scales includes:
There are the following problems. That is, it has been found that in animal fibers, there is a cell membrane complex that joins each Mi fiber cell, albeit in a very small amount, and when this complex is eluted, it has an important effect on the functionality of the fiber. In particular, when this method 4) is applied, the bonding force between each tissue decreases, resulting in a decrease in fiber strength, and the small swelling difference between ortho and bara cortex decreases, resulting in uniform swelling. As a result of this, there is a noticeable decrease in the appearance of crimp, and furthermore, as a matter of course, the removal of cell membrane complexes causes a decrease in water swelling.
It is said that the swelling function of the scale is reduced, the prominence of the scale is suppressed, and as a result, some shrink-proof properties are obtained.

[Problem to be solved by the invention]

Conventional shrink-proofing methods such as those described above have attempted to only prevent felting while damaging the original properties of animal fibers. As a result, the following problems have arisen.

1) The original characteristics of animal fibers, which are both water absorption and water repellency, are inhibited, and the fibers are modified into water absorbent fibers that absorb water quickly.
In addition, moisture is released quickly and heat transfers rapidly, resulting in fibers that lack heat retaining properties, and further affects stain resistance, electrostatic charging properties, and dyeability.

2) Shrink-proofing treatment involves strong chemical treatment, which inevitably makes it easier for cell-to-cell complexes to elute, which reduces the bonding ability between tissues and reduces the mechanical strength of the fibers. It's remarkable.

3) Due to the elution of the cell membrane complex, the mechanical responsiveness of the fibers on elongation-recovery decreased, resulting in a decrease in the occurrence of crimp, and a decrease in bulkiness, air permeability, and compressive elasticity. When modified into fibers, in particular, the reduction in bulkiness affects the reduction in air content, thus inhibiting the role of low heat conduction of air, and also having a negative effect on water vapor diffusion. The clothing performance is also unsatisfactory from a consumer standpoint.

In order to solve these problems, the present invention solves these problems by crosslinking scales with a polymer without reducing water repellency and while protecting the inside of the fibers. This is what I am trying to do.

[Means and effects for solving the problem] The method for epoxidizing animal fiber materials of the present invention involves moistening the material containing animal fibers with a first stage treatment bath consisting essentially of a saturated aqueous solution of a neutral salt. - membrane swelling treatment, then reduction treatment using a second stage treatment bath prepared by adding a reducing agent to the first stage treatment bath, then adding an epoxy compound to the second stage treatment bath; This includes crosslinking polymerization treatment using the prepared third stage treatment bath.

That is, the present invention aims to provide a novel processing method that is completely different from the above-mentioned methods 1) to 4) that have been considered up to now.

When animal fibers, such as wool, are immersed in water, the scaly scales bulge, increasing the anisotropy of the coefficient of friction.
This is why it is felted.

Therefore, if it is possible to set and fix the space between the scales so that the scales do not bulge in water, that is, to cross-link and fix the scales with a hydrophilic polymer, it is possible to improve water repellency and water absorption. The swelling of scale in water is prevented, and as a result, felting does not occur, without any loss in the original properties of wool fibers, including moisture wicking properties. Fortunately, a cell membrane complex exists between the scales of animal fibers, and this plays the role of joining each tissue, but this component is a hydrophilic non-keratin protein with few cystine cross-links. It is highly swellable with water and acts as a waterway for water penetration. Therefore, by fixing this composite, it is possible to naturally prevent the scale from rising in water, and as a result, the animal fiber material does not become felted, which is the original idea of the present invention.

That is, in order to solve the problems of the present invention, the following three requirements are required: (1) The reaction must be carried out in a state where the scale does not rise in water.

2) Do not impair the water repellency of the epicuticle of the scale epidermis.

3) Bridging the scales by reacting with the cell membrane complex between the scales.

must be satisfied. A dry cleaning method is widely known as a method for washing animal fibers, such as wool fibers, without forming them into felt.

Since this dry cleaning is performed in a non-aqueous system, it is possible to naturally suppress the scale from rising due to water. In normal water-based treatment, it is inevitable that scale will rise and become felt due to the action of water. However, when animal fibers are soaked in a saturated aqueous solution of neutral salt and subjected to a felting test using an Ernfelt Ball tester, it is found that felting is significantly suppressed. This is because the water within the fibers moves to the outside of the fibers, causing membrane swelling of the entire fibers, which naturally results in suppression of scale protrusion.

Table 2 shows the felting of wool fibers using aqueous sodium chloride solutions of various concentrations.

Table 2 Relative values of felted ball density of wool fibers at various concentrations of aqueous sodium chloride solution 60 minutes Shaking 1.00 0.81 0.60 0.52 Concentration of sodium chloride (%, wt/ν) 0 (Pure Water) 20.0 24.0 26.5 (Saturated aqueous solution) Notes = 1) Fell I ball density of untreated wool [(u'r=
0.1268g/c-d) was set as 1.

2) The felt ball test consists of 1. W, T, O, Test
Methods 20-69 was followed.

As is clear from Table 2, wool fibers deswell in a saturated aqueous solution of neutral salts, and as a result, felting is suppressed. It is widely known that when wool fibers are reacted with an oxidizing agent such as potassium permanganate in this saturated aqueous solution, the oxidizing agent reacts only with the epidermal tissue of the wool fibers and protects the inner tissue of the wool fibers.

In the method of the invention, a saturated aqueous solution of a neutral salt is utilized for the reaction of animal fibers with a hydrophilic polyfunctional epoxy compound.

In the method of the present invention, the most suitable neutral salts are sodium chloride, sodium sulfate, and sodium carbonate, and these neutral salts are used as catalysts for the reaction between animal fibers and hydrophilic polyfunctional epoxy compounds. is also valid. In terms of this catalytic effect, the reaction rate of epoxy groups increases in the order of sodium sulfate, sodium chloride, and sodium carbonate, that is, in the order of basicity and electronegativity, but considering temperature differences in solubility, etc. Using sodium chloride is highly effective in practical terms.

The concentration of a saturated aqueous solution of sodium chloride is 2 at 0°C.
6.28wt%, and at 80°C, 27.54wL
%.

In the first step of the method of the present invention, as mentioned above, a material containing animal fiber (hereinafter simply referred to as animal fiber material) is
The first treatment bath consists essentially of a saturated aqueous solution of a neutral salt. This first stage treatment is preferably carried out at 30°C
It is carried out at a temperature of 50"C1, more preferably 35 to 45"C, preferably for 10 to 30 minutes, more preferably for 15 to 25 minutes. In addition, there is no particular restriction on the bath ratio of the animal fiber material and the first stage treatment bath, but -a is 1:10 to 1
:30 is preferable. This first stage treatment causes the animal fibers to become wet membrane swollen, so that the scale on the fiber surface does not rise.

In the second stage of the process according to the invention, a reducing agent is added to the first stage treatment bath and the animal fiber material is treated with the second stage treatment bath thus prepared.

The reducing agent used in the present invention is preferably selected from sodium acid sulfite, sodium sulfite, and sodium periosulfate.

The concentration of the reducing agent contained in the second stage treatment bath is preferably 1
% to 5%-t/v, and the bath ratio of the animal fiber material to the second stage treatment bath is generally preferably 1:10 to 1:30. The second stage treatment is preferably at a temperature of 30"C to 50C, more preferably 35 to 45C, preferably 10
-30 minutes, more preferably 15-25 minutes.

The reduction treatment of the present invention protects the interior of animal fibers and removes disulfide cross-links (-SS-
) and convert it into a cysteine group (-3H). The cysteine groups formed in the animal fiber epidermal tissue form crosslinking polymerization (side) in the next stage of epoxy crosslinking polymerization reaction.

In the third step of the method of the invention, the reduced animal fiber material is treated by adding an epoxy compound to the second treatment bath to prepare a third treatment bath.

As the epoxy compound used in the present invention, preferably a hydrophilic polyfunctional glycidyl ether compound, more preferably a glycerol glycidyl ether compound is used.

Such an epoxy compound is preferably 200
Those having an average molecular weight of ~1,000, more preferably about 270, and an average number of epoxy functionalities preferably from 1 to 6, more preferably from 2 to 6 are used.

The concentration of the epoxy compound in the third stage treatment bath is preferably 1-5% wt/v, more preferably 2-3%-t/v, and the animal fiber material is mixed with the third stage treatment bath. The ratio is 1:
In the third stage treatment bath, which is preferably 10 to 1:30, the neutral salt and the reducing agent function as catalysts for the reaction between the animal fiber and the epoxy compound; , more preferably 0.5
~2%-t/v, more preferably about 2.5-3.5%
Wt/v zinc borofluoride may be included as a catalyst.

The crosslinking polymerization treatment in the third stage treatment is preferably 60 to
At a temperature of 75-85°C, more preferably 90°C5, preferably 30-90 minutes, more preferably 50-70°C.
It takes place for a minute.

The epoxy compound used in the method of the present invention is preferably hydrophilic. Generally, when the crosslinked polymer is hydrophobic, the hygroscopicity, water absorption, and moisture release properties of animal fibers are inhibited.

In the method of the present invention, a treatment with a polyfunctional epoxy compound is performed to form three-dimensional crosslinks between scales. As this epoxy compound, it is preferable to use, for example, Bunacol Eχ313□314, manufactured by Nagase Kasei Co., Ltd., which is glycerol polyglycidyl ether and has an average molecular weight of 270 and an average number of epoxy functional groups of 2.0, in order to enhance the effect of this treatment. there were. However, even if animal fibers, such as wool fibers, are immersed in a saturated aqueous solution of sodium chloride, an epoxy compound is added to the treatment solution, and the temperature is raised to 80"C to react with the animal fibers, It is not possible to prevent felting.

Table 3 shows an example of the influence of the reaction medium on the amount of the epoxy compound (Bunacol EX) deposited on the wool fibers and the density of the resulting felt balls.

Table 3 Effect of reaction medium and felt ball density on adhesion it (%) of epoxy compound Untreated water 4.5 1.0 1.25 Notes: 1) Felt ball density of untreated wool (UT-0,
1268g/co! ) was calculated as ■.

2) Put the wool fiber in a saturated aqueous solution of sodium chloride at 40°C, then add 5%-t/v Bunacol Eχ313, raise the temperature to 80°C, treat for 60 minutes, wash with water, and dry. did.

From the results in Table 3, it can be seen that a saturated aqueous solution of sodium chloride has about twice the catalytic effect in the epoxy treatment, as seen from the increase in the amount of wool fibers attached, but it is not effective in preventing felting. It can be seen that there is no effect.

In the method of the present invention, it has been found that very good results are obtained when wool fiber material is reduced with acidic sodium sulfite in a saturated aqueous solution of sodium chloride and then treated with epoxy in the same bath. It was.

Table 4 shows an example of the effect of a reducing agent (acidic sulfite) in the treatment of wool fibers with a sodium chloride saturated aqueous epoxy compound treatment solution.

Beneath margin Table 4 Effect of acidic sulfite on epoxy treatment of saturated aqueous sodium chloride solution Notes? 1) Felt ball density of untreated wool (UT=0,
1268 g/cIll) was calculated as 1.

2) Place wool fibers in saturated aqueous sodium chloride solution at 40°C, then add 5% wt/v Bunacol Ex313 and 3%
- adding t/v of sodium acid sulfite (no addition),
The temperature was raised to 80°C, treated for 60 minutes, washed with water, and dried.

3) S) IIM of untreated wool is 10 r/gwool, and on reduction treatment with acidic sodium sulfite in a saturated aqueous solution of sodium chloride, it is 55, IIM/g
It was 1 volume.

When animal fibers, such as wool fibers, are reduced with acidic sodium sulfite in a saturated aqueous solution of sodium chloride to reduce disulfide (SS) crosslinks in the epidermal tissue, cysteine groups (SH) are generated.

This S 2 H group has very high chemical reactivity and reacts rapidly with an epoxy compound, and the epoxy compound having hydrophilic polyfunctionality easily undergoes three-dimensional crosslinking polymerization using the generated SH group as a starting point. As a result, it is possible to fix the cell membrane complex existing between the scales and prevent the scale from rising in water.

In general, it is well known that the crosslinking polymerization of epoxy compounds is promoted when a catalyst is used due to the basicity and/or electronegativity.However, sulfite used as a reducing agent also is an important catalyst for
The role of this sulfite is to increase the number of crosslinking sites for the epoxidation reaction and further promote crosslinking polymerization. This reduction treatment makes it possible to epoxidize cell membrane complexes that are hydrophilic and have a low SS crosslink density (non-keratin proteins), increase the epoxy crosslink density, and cross-link and fix between scales. As a result, it has become possible to suppress water swelling of the cell membrane complex, prevent scale protrusion, and prevent felting.

The reducing agent used in the reduction treatment in the method of the present invention also acts as a catalyst for the epoxidation reaction.

Sodium sulfite and sodium thiosulfate, which have a strong basicity, are good for silk fibers, but for wool, they are reduced at 40°C in a saturated aqueous solution of neutral salts, and then treated with epoxy at 80°C. Under conditions such as those conducted in a bath, hydrolysis is likely to occur, so the reaction conditions should be slow (50°C to 60°C).
).

Therefore, the most suitable reducing agent for the method of the present invention is sodium acid sulfite.

Suitable catalysts for the epoxidation reaction include acidic sodium sulfite, sodium sulfite, sodium thiosulfate, zinc borofluoride, and tin chloride. For example, wool fibers are reduced with acidic sodium sulfite at 40°C for 520 minutes, and then the epoxy compound specified in the present invention is added to the same bath, and further 0.1%-L/v to 2%-t Zinc borofluoride, preferably about 1% 4/v, is added to the third stage treatment bath, heated to 80°C and treated for 30 to 90 minutes, optimally for 60 minutes. is desirable.

Further, as a method of adding the reducing agent, half of the total amount used may be added to the reduction treatment step, and the remaining half amount may be added to the epoxy treatment step.

After the epoxidation reaction treatment, it is deliquified, washed with hot water at around 40°C and then washed with cold water, which is repeated, and dried at 80°C to 110°C, preferably 85°C.

The animal fiber used in the method of the present invention preferably has keratin protein as its main component and has scaly scales in its epidermal tissue, and includes wool, angora, cashmere,
It is preferable to use animal hair such as llama, vicuña, albaca, camel, and mohair.

The animal fiber material may be in the form of loose hair, top, yarn, weave, etc.

〔Example〕

The present invention will be specifically explained by examples.

As the lining soil animal fiber, Australian white wool top tog was mixed with sodium chloride (salt) 1 prepared in advance using a 12-color color bed manufactured by Nippon Senkiki Co., Ltd.
12g and 0.1%-t/v permeate side, Tergitol
The sample was loaded into a container containing 300 mL of a saturated sodium chloride aqueous solution (first stage treatment bath) consisting of TMN (manufactured by Union Carbide), and immersed at 40°C for about 10 minutes. Next, 2
%-t/v of sodium acid sulfite was added to the first stage treatment bath and the wool top was reduced in this second stage treatment bath at 40°C for 20 minutes. Next, add 3% wL of epoxy compound, Bunacol 313 (manufactured by Nagase Chemical Industries, Ltd.).
/v, 2%-t/v sodium acid sulfite and 1% wt/v zinc borofluoride as catalysts were added to the second-stage treatment bath, and the resulting third-stage treatment bath was ℃/win 80°
The temperature was raised to C and the wool top was treated at this temperature for 60 minutes. After the epoxidation reaction treatment, the wool top was dehydrated and
It was thoroughly washed with hot water, cold water, and dried in a hot air dryer at 85°C. The felt properties, water repellency, and compression resistance of the epoxidized wool were measured and are shown in Table 5.

Table 5 Performance of epoxidized wool Treatment Felt ball density Water repellency Compression resistance 6
0 minute shaking sec kg/yt 2.5
“c4 unprocessed 1 >24h
3.50 Note: 1) Measurement of felt ball density: I
The method of ,W,T,O,TestMethod 20-69 was followed. Felt ball density of untreated wool (
UT=0, 1268 g/cd) was taken as 1.

2)? 9 Aqueous test: 1 g of the sample was opened, 300 l of distilled water was poured into a 500 m1 beaker, the sample was placed on the liquid level, and the sinking speed was measured.

3) Measurement of compression resistance force: Using the piston-cylinder method, put 2.5g of the sample into a container with a diameter of 5c+a, and measure the force required to compress the fiber packing density from 42.5■/d to 127.5mg/m. It was measured.

4) In the CI/1lercosett treatment, the object to be treated is chlorinated in a batch manner with an amount of active chlorine of 1.8% owf, and after dechlorination, hydrophilic cations are added so that the amount of adhesion is 2.0% owf. System 1 (by treatment with ercosett resin).

1 kg of Reno 60°S) was charged into a high pressure dyeing machine (capacity 12 kg) manufactured by Nippon Senzoki Co., Ltd. with the yarn laid down in a layered manner, and treated in the same manner as in Example 1. The bath ratio was 1:10, and the drugs, drug amounts, and prescriptions were all as described in Example 1.

The obtained wool knitted yarn was knitted into a warm cloth with a density of 0.41, and its washing resistance and yarn strength were measured.

The results are shown in Table 6.

Table 6 Washing resistance and yarn strength of treated worsted stockinette yarn As is clear from the results shown in Table 5, wool fibers treated according to the method of the present invention have a high degree of shrink resistance without impairing their water repellency. was able to be obtained, and furthermore, its compression resistance was significantly improved.

JJt example - Worsted stockinette yarn 2/3 ONm as turtle animal fiber (untreated 7.3 60.9 80.0 88.0 375.6 14.8
Note: 1) Washing resistance test was conducted using IWS Te5t Met
Tested according to hodsTM-31, 1980.

2) A TLster continuous strength tester was used for the yarn strength test.

According to the IWS test standards, if the area shrinkage rate is 10% or less in three repeated washing tests using washing test method 5, it is said that the product has sufficient washing resistance as outer lid clothing.

However, the animal fiber materials treated according to the embodiments of the method of the present invention fully passed this standard, and the mechanical strength of the fibers was further improved.

10 g each of cashmere and angora fibers as animal fibers were treated according to the same method as in Example 1.

After treatment, felt ball density was measured. The results are shown in Table 7.

Margin below Table 7 Epoxy treatment of cashmere and angora fibers Note: l) Measurement of felt ball density is as follows: 1. W, T, O.

Te5t Methods 20-69 was followed.

2) Untreated felt ball density (cashmere 1JT=0
．． 1039 g/c, Angola tlT=0.090
9g/cui) was calculated as ■.

Until now, it has been a very difficult task to apply shrink-proofing treatment to cashmere and angora without impairing their texture or reducing the water repellency of their surfaces. but,
When treated according to the method of the present invention, the intended purpose can be fully achieved, and it has become possible to impart high washing resistance to cashmere wool blends and angora wool blend materials.

[Effects of the Invention] The method of the present invention provides the following advantages: 1) without impairing the water repellency of the epidermis, which is one of the original characteristics of animal fibers, 2) while protecting the cortical tissue inside the fibers, and 3) improving the mechanical properties of the fibers. 4) without affecting the hygroscopicity, water absorption and water release properties of the fibers; 2) improving fiber strength; and 6) preventing scale from rising in water. A high degree of shrink resistance can be imparted to the material. In addition to this,
1) Treatment with a reducing agent, such as sodium acid sulfite, bleaches the animal fiber material and imparts gloss at the same time; 2) Improves pilling properties due to improved shrink resistance; 3)
) Since the epidermal tissue is strengthened by blocking functional groups with epoxy compounds, improvements in chemical resistance, insect repellency, light resistance, and mold resistance are also expected.

The basis of the method of the present invention is that the first stage pretreatment is performed using a saturated aqueous solution of a neutral salt such as sodium chloride to bring the inside of the fiber into a membrane-swollen state to suppress the penetration of chemical agents.
The second and third stage treatments are concentrated only on the surface of the fibers, thereby preventing a decrease in the mechanical strength of the fibers and removing cystine (SS) in the hydrophilic cell membrane complex region that exists between the scales. ) cross-links are reduced by a reducing agent to form cysteine (S R), which is highly reactive S
The point is that crosslinking polymerization is carried out with an epoxy compound using H groups as reaction sites and using a neutral salt, a reducing agent, and, if necessary, zinc borofluoride as a catalyst. Epoxy compounds are said to bond with aliphatic hydroxyl groups, aromatic hydroxyl groups, carboxyl groups, amino groups, imino groups, etc., but as in the present invention, crosslinking polymerization of epoxy compounds between scales is attempted. In this case, the crosslinking density and water swelling property of the proteins forming the epidermal tissue are closely related to this crosslinking polymerization reaction, and the formation of cysteine (S)() in the epidermal tissue is an important factor. This is where the characteristics and basics of the method of the present invention lie.

Until now, considerable research has been carried out on the shrink-proofing of wool fibers, but a fully satisfactory level has not yet been reached. On the other hand, with respect to high-quality animal hair such as cashmere, angora, etc., almost no research has been conducted on anti-shrink treatment. This clearly shows that the formulation used as a shrink-proofing method for wool fibers cannot be applied to these high-quality animal hair fibers. The method of the present invention is applicable to the modification of these high-quality animal hairs. For example, in the case of cashmere fibers, the fibers are thin and have a unique texture.
However, these fibers have problems such as being easily felted, having poor pilling resistance, and low elasticity, and the elasticity significantly decreases when water is absorbed. For the first time, the method of the present invention has made it possible to improve the shrink-proofing properties, pilling resistance, elasticity, etc. without causing any damage.

The embodiments of the method of the present invention are summarized as follows.

1. The neutral salt is sodium chloride, sodium carbonate,
and sodium sulfate.

2. The method of claim 1, wherein said wet-swelling treatment is carried out at a temperature of 30-50''C.

3. The method of claim 1, wherein the reducing agent is selected from sodium acid sulfite, sodium sulfite, and sodium thiosulfate.

4. The method of claim 1, wherein the reduction treatment is carried out at a temperature of 30-50''C.

5. The concentration of the reducing agent in the second stage treatment bath is 1 to 5%.
2. The method of claim 1, wherein the method is wt/v.

6. The method according to claim 1, wherein the bath ratio (weight) of the animal fiber material and the second treatment bath in the reduction treatment is 1:xo-t:3o.

7. The reduction treatment reduces the disulfide crosslinks (-SS-) present in the cell membrane complex region that exists between the scales of the epidermal tissue of animal fibers, and reduces the cysteine group (-SS-).
-3H).

8. The method according to claim 1, wherein the epoxy compound is selected from hydrophilic polyfunctional glycidyl ether compounds.

9. The method according to claim 1, wherein the epoxy compound is selected from glycerol glycidyl ether compounds.

10. The method according to claim 1, wherein in the crosslinking polymerization treatment, the concentration of the epoxy compound in the third treatment bath is 1 to 5%-t/v.

11. The method according to claim 1, wherein the crosslinking polymerization treatment is carried out at a temperature of 60 to 90°C.

12. The third stage treatment bath further contains 0.5 to 2%-t/v
2. The method of claim 1, comprising zinc borofluoride.

13. The method according to claim 1, wherein the animal fiber has keratin protein as its main component, and its epidermal tissue has scaly scales.

14. The method of claim 1, wherein the animal fiber is selected from wool, angora hair, cashmere hair, llama hair, vicuña hair, albaca hair, camel hair, and mohair hair.

15. The method of claim 1, wherein the animal fiber material is selected from loose hair, tops, threads, and knits.

16. The cross-linked polymerized animal fiber material undergoes dehydration,
The method according to claim 1, wherein the method is washed with water and dried.

Claims (1)

[Claims] 1. A material containing animal fibers is subjected to a wetting-deswelling treatment in a first stage treatment bath consisting essentially of a saturated aqueous solution of a neutral salt, and then to the first stage treatment bath. A reduction treatment is performed using a second stage treatment bath prepared by adding a reducing agent, and then a crosslinking polymerization treatment is performed using a third stage treatment bath prepared by adding an epoxy compound to the second stage treatment bath. , a method for epoxidizing animal fiber materials.