JPH05179574A - Method for improving animal hair fiber subjected shrink proofing - Google Patents

Abstract

PURPOSE:To carry out improvement and shrink proofing maintaining hydrophilic nature like virgin animal hair fibers and excellent physical properties of fiber such as strength and elongation by treating animal hair fibers subjected to shrink proofing with a polyamino acid. CONSTITUTION:Animal hair fibers subjected to shrink proofing prepared by oxidation treatment are immersed in a processing solution containing a polyamino acid or the polyamino acid and a crosslinking agent (e.g. isocyanate crosslinking agent and epoxy-based crosslinking agent), then coagulated and a coating film of the polyamino acid is formed on the surface of the animal hair fibers to give animal hair fibers subjected to shrink proofing having characteristic hydrophobic nature of animal hair while retaining a characteristic natural animal hair-like handle of polyamino acid. The polyamino acid, for example, is obtained by decarbonating and polymerizing an amino acid N-carboxylic acid anhydride.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for modifying shrink-proof animal hair fibers by modifying properties such as hydrophobicity, moisture permeability and fiber physical properties of the shrink-proof animal hair fibers.

[0002]

2. Description of the Related Art Animal wool cloth has a drawback that it shrinks greatly when washed at home and becomes felt, and various shrink-proofing methods have been developed in order to improve this. For example, there are methods a), i), u), and e) below. A) Use the animal hair fiber cuticle as sodium hypochlorite,
A method of desorbing with a chlorinating agent such as sodium dichloroisocyanurate and an oxidizing agent such as monopersulfuric acid or potassium permanganate. B) After the animal hair fiber cuticle was treated with chlorinating agent
Method of coating with polyamide epichlorohydrin resin. U) A method of coating a cuticle of animal hair fiber with a synthetic polymer. E) A method of reducing the anisotropy of the friction coefficient of animal hair fibers by modifying the fiber surface by low temperature plasma treatment, corona discharge treatment, etc.

The above methods a), i) and u) are actually industrialized. A) and i) are currently the most widely used shrink-proofing treatments, but the fibers themselves are damaged by the treatment with chlorinating agents and oxidants, and the hydrophobic properties peculiar to animal hair fibers are lost and they become hydrophilic. At the same time, there is a drawback that the fiber performance is deteriorated. With regard to (4), the treatment form is limited to the treatment of animal fabrics in order to obtain satisfactory shrink resistance, and the texture is poor. The method (e) has not been industrially used yet, but the fiber itself has lost hydrophobicity and has become hydrophilic as in (a).

[0004]

DISCLOSURE OF THE INVENTION The present invention is intended to solve such problems, and is a virgin animal hair fiber while maintaining the natural texture of the animal hair fiber peculiar to polyamino acid while being a shrink-proof animal hair fiber. It is intended to impart additional properties such as hydrophobicity and fiber properties such as excellent strength and elongation, and excellent moisture permeability.

[0005]

Means for Solving the Problems As a result of intensive studies on the method for modifying shrink-proof processed animal hair fibers, the present inventor has found that cuticles damaged by shrink-proof processing have polyamino acids or polyamino acids having the same composition as animal hair fibers. By treating animal hair fiber with a cross-linking agent and maintaining the animal hair-like texture peculiar to polyamino acids, it has excellent shrinkage resistance and is as hydrophobic and strong as virgin animal hair fiber. The inventors have found that additional performance such as degree can be imparted, and have completed the present invention. That is, the present invention provides (1) a method for modifying shrink-proof animal hair fibers, which comprises treating the shrink-proof animal hair fibers with a polyamino acid. (2) A method for modifying a shrink-proof animal hair fiber, which comprises treating the shrink-proof animal hair fiber with a polyamino acid and a crosslinking agent. Consists of.

The present invention will be described in detail below. The animal hair fiber in the present invention means a natural keratinous fiber obtained from animals such as sheep, cashmere, mohair, angora, camels, and alpaca, and the fiber form thereof is animal hair alone,
Alternatively, it is a sliver, thread, woven fabric, knitted fabric, non-woven fabric, etc. containing at least 15% of animal hair.

The shrinkproofing method for animal hair in the present invention comprises pretreatment for oxidation, reduction neutralization treatment and resin treatment. First, the oxidization conditions should be adjusted depending on the type of animal hair fiber, and usually varies depending on the type of oxidizer and the amount used, but when generally carried out by a batch method, 1 to 10% o. w. f. After the immersion treatment at room temperature for 10 to 30 minutes, the temperature is raised to 30 to 50 ° C. and the treatment is performed for 10 to 40 minutes. If the continuous method is used,
10% o. w. f. At room temperature for about 2 to 15 seconds,
After squeezing the solution with a pickup of 100%, it may be allowed to stay at room temperature for about 3 to 5 minutes. Such processing temperature and processing time are merely a guideline and are not necessarily limited thereto.

Examples of the oxidizing agent used here include hypochlorite, chlorite, dichloroisocyanurate, potassium permanganate, hydrogen peroxide, monopersulfuric acid, and salts thereof. it can.

The animal hair fiber that has been subjected to the oxidation treatment is thoroughly washed with water, and then the oxidizing agent remaining inside the fiber is neutralized and removed by using a reducing agent. As the reducing agent, sodium bisulfite, sodium sulfite, sodium metabisulfite, or the like can be used, and the used amount thereof is 3 to 10% o. w. f. The degree is appropriate.

The animal hair fiber which has been subjected to the reducing agent neutralization treatment is washed with water and then a cationic polyamide epichlorohydrin resin, an aminoacryl copolymer or the like is applied to the animal hair fiber to be exhausted. A typical aminoacrylic copolymer is (MMA) x: (DMAEMA) y quaternized with myristyl bromide, (MMA) x:
(DMAEMA) y quaternary compound with epichlorohydrin, (MMA) x: (vinylpyridine) y quaternary compound with epichlorohydrin, (IBMA) x: (DMAPM)
There are quaternized products of epichlorohydrin of A), quaternized products of (methacrylamide) x: (DMAPMA) with epichlorohydrin, and the like. However, in the above, MMA is methylmethacrylate, DMAEMA is dimethylaminoethylmethacrylate, DMAPMA is dimethylaminopropylmethacrylamide, and x: y is 10 to 1: 1.
Is a compound in the range. The polyamide epichloroedrin resin has a pure content of 0.5 to 2.0% o. w.
f. , Aminoacrylic copolymers have a pure content of 0.4 to 1.0% o. w. f. Is desirable.

If necessary, the animal hair fibers which have exhausted the resin are provided with a softening agent and then at a temperature of about 80 ° C. for 5 to 30.
Drying is performed for a minute to obtain a shrink-proof processed animal hair fiber. As described above, the shrink-proof processed animal hair fiber of the present invention is an animal hair fiber that has been subjected to shrink-proof processing by the oxidation / resin method.

The polyamino acid used in the present invention is obtained by decarboxylation polymerization of amino acid N-carboxylic acid anhydride (hereinafter referred to as NCA) using an initiator in an organic solvent.
Typical examples thereof are γ-methyl glutamate, γ-ethyl glutamate, γ-benzyl glutamate, β-methyl aspartate, β-ethyl aspartate, β-benzyl aspartate, valine, norvaline, leucine, isoleucine, norleucine, phenylalanine,
Mention may be made of NCA such as methionine, glycine and alanine, and any optically active or racemic form thereof may be used, and copolymers of two or more of these and NCA.
Further, a polyamino acid obtained with the above initiator may be a copolymer obtained by a chain extension reaction with an isocyanate compound, a urethane prepolymer having an isocyanate at the terminal, or the like. If necessary, it may be a block or random copolymer with other polymers. However, the amino acid composition of the copolymer is preferably 30% by weight or more, more preferably 60% by weight or more in order to maintain the characteristics of the polyamino acid.

As the organic solvent used for the polymerization of NCA,
N, N-dimethylformamide, formamide, N, N
-Dimethylacetamide, N-methylpyrrolidone, dioxane, tetrahydrofuran, diglyme, benzene,
Toluene, xylene, methyl ethyl ketone, etc. may be mentioned, and these solvents may be used alone or in a mixed system. If necessary, these organic solvents may be used for dilution after the polymerization.

The initiator used in the present invention is a compound having active hydrogen such as amino group and hydrosyl group. For example, ammonia, monomethylamine, dimethylamine, diethylamine, ethylenediamine, propylenediamine, hexamethylenediamine, 1,4-cyclohexanediamine, o-phenylenediamine, p-phenylenediamine, toluene-2,4-diamine, 4,4'-
Diphenylmethanediamine, polyoxypropylenediamine, N, N-dimethylethylenediamine, N, N-dimethyl-1,3-propanediamine, isophoronediamine, 1,2-cyclohexanediamine, polysiloxane having primary and secondary amino groups, polybutadiene Compounds and other amino compounds, ethylene glycol, 1,3-butanediol, hexamethylene glycol, polyester diol, alcohols such as hydroxyl group-containing polysiloxane and polybutadiene compounds, and urethane prepolymers such as amine at both ends Can of course also be used. It is also possible to copolymerize a urethane prepolymer having isocyanate at both ends with NCA using the above-mentioned initiator.

The polymerization initiator is 0.01 to 1 with respect to NCA.
0 mol%, preferably 0.1 to 2 mol% is used. Also,
If necessary, a tertiary amine such as trimethylamine, triethylamine or tributylamine can be used in combination.

Examples of the cross-linking agent include isocyanate-based cross-linking agents and epoxy-based cross-linking agents represented by the following formulas 1 to 10. The addition amount is 0.1 to the polyamino acid solid content.
It is 1 to 30% by weight, preferably 3 to 10% by weight.

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

Further, the method for modifying the shrink-proof animal hair fiber according to the present invention can be carried out as follows. 1) Animal hair fibers are immersed in a solution of polyamino acid (concentration of 0.1 to 10%), and a polyamino acid film is formed on the animal hair fiber surface by wet or dry coagulation to perform modification processing. 2) A cross-linking agent is added to a solution of polyamino acid (concentration: 0.1 to 10% by weight) in an amount of 0.1 to 3 based on the solid content of the polyamino acid.
The processing liquid is added in an amount of 0% by weight, and the animal hair fiber is dipped and modified by wet or dry coagulation to form a polyamino acid film on the animal hair fiber surface. 3) After immersing the animal hair fiber in a solution having a crosslinking agent concentration of 0.1 to 30% by weight, further immersing it in a solution of polyamino acid,
In the same manner as in 1), a modification treatment is performed by forming a polyamino acid film on the surface of animal hair fiber. 4) After forming a polyamino acid film on the animal hair fiber surface,
Further, it is immersed in a cross-linking agent solution for modification processing.

Although any of 1) to 4) can be used for processing, 1) and 4) are slightly inferior to 2) and 3) in adhesiveness between animal hair fiber and polyamino acid film. In addition, since 3) has complicated steps, 2) is proposed.

[0029]

[Function] Generally, by treating with a polyamino acid or a polyamino acid and a cross-linking agent, a film can be coated on the surface of shrink-proof processed animal hair fiber, and the animal hair can be produced while maintaining the animal hair-like texture peculiar to polyamino acid. It is possible to impart excellent shrink resistance and hydrophobicity.

Further, after pretreatment with an oxidizing agent, a shrink-resisting animal hair fiber to which a cationic resin such as epichlorohydrin resin is applied has a cationic resin coated on the fiber surface, which is reactively bonded with an active group such as a carboxyl group of polyamino acid. Therefore, the cationic resin acts as a cross-linking agent between the animal hair fiber and the polyamino acid resin, and as a result, a uniform film of the polyamino acid resin is formed on the surface of the shrink-proof processed animal hair fiber, and by the oxidant pretreatment, Damaged cuticles can be regenerated.

[0031]

EXAMPLES The present invention will be described in more detail below with reference to examples. Synthetic example Polyamino acid synthesis In a reactor equipped with a stirrer, 500 parts of polytetramethylene glycol with an average molecular weight of 2000 (manufactured by Sanyo Kasei Co., Ltd.), 111 parts of isophorone diisocyanate, and 0.22 parts of a 10% toluene solution of dibutyltin dilaurate as a catalyst. In addition, 120 ℃
The temperature was raised to and the mixture was stirred for 3 hours. Then after cooling to 70 ° C,
DMF (611 parts) was added to obtain a 50% solution (designated as 1a) of both terminal isocyanates. Next, 300 parts of polypropylene ether diamine (trade name: Jeffamine D-2000) and 900 parts of DMF were added to a reactor equipped with a stirrer, and 494 parts of the above 1a and 494 parts of DMF were added thereto at room temperature. After stirring for 3 hours, an initiator I of both terminal amines (amine value 2980) was obtained.

Next, 40 parts of the above-mentioned initiator I, 420 parts of DMF and 450 parts of dioxane were added to a reactor equipped with a stirrer, and then 88.3 parts of NCA of γ-methyl-L-glutamate, L.
-Add 31.3 parts NCA of leucine and add triethylamine 0.
After 66 parts were added and the mixture was stirred at room temperature for 30 minutes, the temperature was raised to 60 ° C. and the mixture was further stirred at that temperature for 3 hours. After confirming that the absorption of NCA disappeared by IR, the reaction was regarded as the end point.

Example The polyamino acid solution obtained in the synthesis example was diluted to 0.5% by weight with methyl ethyl ketone, and 8% of coronate EH as a cross-linking agent was added to the polyamino acid solid content to prepare a working fluid.

An Australian 66 merino wool sliver was dipped in the above processing liquid for about 10 to 15 seconds, squeezed with a mangle so that the pickup rate would be 110%, and washed with water in the first tank of the backwasher at 20 ° C. 60 in 2 tanks
After washing with hot water at ℃, a polyamino acid film was formed by performing a drying treatment at 80 ℃. Using the polyamino acid-processed sliver thus obtained, a knitted yarn of 2/60 count was spun, and the fiber performance of the polyamino acid process was evaluated by the following test method. As a comparative sample, the same wool sliver used for processing polyamino acids was previously prepared with sodium dichloroisocyanurate 3.5% o. w.
f. Is added and the solution is immersed at 25 ° C. for 25 minutes, washed with water, and then sodium sulfite 10.0% o. w. f. Chlorinated wool sliver obtained by adding 15 to 30 ° C. for 15 minutes at 35 ° C. and thoroughly washing with water, and Hercoset 57 (manufactured by Dick Hercules, polyamide epichlorohydrin resin) after chlorination by the above method ) Is 20% o.
w. f. Take it, add it to the treatment bath after diluting it well,
The results of the chlorinated / resin-treated wool sliver obtained by performing the heat treatment at 30 ° C. for 30 minutes and the dry heat treatment at 80 ° C. for 30 minutes and the knitted fabric obtained from them are also shown. (1) Evaluation of spinning property and binding force of polyamino acid-processed sliver When chlorinated wool is processed with polyamino acid, polyamino acid released from the sliver adheres to the front roller in the pre-spinning process, causing frequent winding. I couldn't spin it up. On the other hand, the chlorinated / resin-treated wool processed could be spun without any trouble such as winding in the spinning process.

It is considered that the difference in the spinnability of these processed slivers is that after chlorination, the cationic resin attached to the fiber acts as a cross-linking agent with the polyamino acid to strengthen the binding force. (2) Hydrophobicity of wool fiber a. Wettability A wool sliver weighing 1 g is adjusted into a ball shape so that the volume is almost equal, and 500 ml from a height of 3 cm on the water surface.
The wettability, that is, the hydrophobicity peculiar to wool, was evaluated by measuring the time required for the sliver to fall completely on the beaker and to completely wet it. The results are shown in Table 1.

[0036]

[Table 1]

Table 1 shows that the addition of polyamino acid to chlorinated wool hardly improves the hydrophobicity, but when applied to chlorinated / resin treated wool, it does not get wet for more than 2 weeks and a hydrophobic film close to virgin wool is formed. It is being reproduced. b. Water absorption (Balex method) Cover factor of 2/60 count knitted yarn 0.
41 flat knitted fabrics according to JIS L1081.5.27. B
Based on the method, the height (mm) of water rising due to the capillary phenomenon after 10 minutes was measured by allowing the lower end of the sample to just come into contact with distilled water, and water absorption, that is, hydrophobicity of wool was evaluated. The results are shown in Table 2.

[0038]

[Table 2]

Table 2 shows that the chlorinated wool and the chlorinated / resin-treated wool have high water absorption, whereas the chlorinated / resin-treated wool treated with polyamino acid has water absorption and hydrophobicity close to that of virgin wool. It shows that the membrane is being regenerated. (3) Weight loss by alkaline protease treatment Protin 3AL (manufactured by Daiwa Kasei, alkaline protease)
5g / L was adjusted to pH8, bath ratio 1:40, temperature 50 ° C
Under the conditions of, a wool sliver weighing 5 g is treated for 5 hours,
The weight loss rate of wool by alkaline protease treatment was evaluated. The results are shown in Table 3.

[0040]

[Table 3]

From Table 3, it can be seen that virgin wool is not easily affected by the alkaline protease, whereas chlorinated wool has a considerably high weight loss rate. On the other hand, the chlorinated / resin-treated wool has a lower weight loss rate than the chlorinated wool, and the polyamino acid-processed wool has a lower weight loss rate, which is close to the weight loss rate of virgin wool. It is speculated that this is because the addition of polyamino acid to chlorinated / resin treated wool results in a composition closer to that of virgin wool. (4) Tensile Strength and Elongation of Yarn The spun knitted yarn of 2/60 count was measured according to JIS L1095.7.5. Table 4 shows the results evaluated by the above test method.

[0042]

[Table 4]

From Table 4, chlorination with polyamino acid added /
It can be seen that the resin-treated wool has the same tensile strength and elongation as the virgin wool, and has been physically restored to the virgin wool. (5) Moisture permeability JIS L1099. Based on the A-1 method, approximately 40 ° C in advance
Put anhydrous calcium chloride as a hygroscopic agent in a warm moisture-permeable cup up to about 3 mm from the upper end of the cup. The test body is placed in a constant temperature and humidity chamber in which air having a temperature of 40 ± 2 ° C. and a humidity of 90 ± 5% RH is circulated, and after 1 hour, the test body is taken out,
Immediately measure the mass a (mg). Next, this test body is put in the constant temperature and humidity chamber again, and after 1 hour, the test body is taken out,
The mass b (mg) was immediately measured, and the moisture permeability was calculated from the following formula. The results are shown in Table 5.

P = [10 × (b−a)] / S where P: Moisture permeability [g / m 2 · h)] S: Moisture permeability area (cm 2).

[0045]

[Table 5]

From Table 5, the moisture permeability of virgin wool and chlorinated / resin treated wool knitted fabric is 323 and 305, whereas the chlorinated / resin treated wool with polyamino acid has high moisture permeability of 399. I understand that. (6) Washing shrinkage resistance A flat knitted fabric with a cover factor of 0.41 in 2/60 count was prepared, and subjected to a relaxation shrinkage of 7A by the IWSTM31 waste skater method, and then a 5A felt shrinkage. The shrinkage resistance to washing was evaluated from the dimensional change. The results are shown in Table 6.

[0047]

[Table 6]

From Table 6, virgin wool is greatly felted due to the anisotropy of the friction coefficient, whereas chlorinated / resin treated wool originally has the shrinkproof property of the super wash standard. It can be seen that the chlorinated / resin-treated wool which has been subjected to the step also naturally has high shrink resistance.

[0049]

As described above, according to the present invention, damaged cuticles can be treated by treating animal hair fibers that have been damaged by shrink-proofing treatment and have become hydrophilic with a polyamino acid or a polyamino acid and a crosslinking agent. Regenerated with polyamino acid that has the same composition as animal hair fiber, while maintaining the natural animal hair-like texture unique to polyamino acid, it is a non-shrinkage animal hair fiber, but it has excellent hydrophobicity like virgin animal hair fiber. Further, it is possible to have additional properties such as fiber physical properties such as high elongation and excellent moisture permeability.

Claims (2)

[Claims] 1. A method for modifying a shrink-proof animal hair fiber, which comprises treating the shrink-proof animal hair fiber with a polyamino acid. 2. A method for modifying a shrink-proof processed animal hair fiber, which comprises treating the shrink-proof processed animal hair fiber with a polyamino acid and a crosslinking agent.