JP2001303438A - Method for treating protein fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent a protein fiber product from yellowing and reduction of its tensile strength and elongation improve its dimensional stability by controlling a hygral expansion behavior without spoiling hand feeling of the protein fiber product, improve the absorbed ratio of a dye and bring reproducibility of dying to be good and obtain the protein fiber product having a high light fastness and bright and clear colors without the appearance of an effect caused by difference in temperature distribution on the treated protein fiber product. SOLUTION: This method for treating a protein fiber product is to bring the protein fiber product to contact with an aqueous treating solution containing 0.05-50 wt.% of a colorless anion-activated material in which 2-3 reactive anionic active groups having either one or both of substitution and/or addition functions capable of reacting with the protein fiber are bonded with the molecular body of an aryl group, subsequently treat the aforesaid protein fiber product in the aqueous treating solution, an air or steam atmosphere at 30-135 deg.C for 1-200 minutes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for treating protein fiber products such as wool. More particularly, the present invention relates to a method for treating protein fiber products in a state of high temperature, high pressure water, steam or plasma, which prevents yellowing of the products and does not reduce the high elongation. The present invention also relates to a processing method for improving shrinkage and wrinkle resistance of protein fiber products and improving dimensional stability. The present invention also relates to a method of treating a protein fiber product by dyeing a protein fiber product using a reactive dye for dyeing the protein fiber product to achieve level and slow dyeing, and to anionize the protein fiber product.

[0002]

2. Description of the Related Art When a protein fiber product is subjected to high-temperature and high-pressure treatment, a dicarboxylic acid is used as a main agent (trade name:
ScaleSet AC, manufactured by Senka Kogyo, or trade name: Basolan 245
4, and those containing formalin as a main agent (trade name: Irgasol HTW, manufactured by Ciba Specialty Chemicals) are conventionally known. In addition, shrinkage prevention of protein fiber products
Conventionally known methods for preventing wrinkles include using a urethane resin or an epoxy resin, or using an organic halogen-based oxidizing agent represented by chlorine gas, a reducing agent containing sulfur, or a phosphine derivative. Further, in order to uniformly dye protein fiber cloth using other reactive dyes for dyeing protein fiber products, a leveling agent mainly containing alkylamine polyglycol ether sulfate (trade name: Albecar A, Ciba Specialty) Chemicals) and leveling agents based on substituted alkylamine polyglycol ethers (trade name:
Conventionally, protein fiber products are treated by selectively using a protein fiber product to be stained with Albecar B (manufactured by Ciba Specialty Chemicals) and another buffer. Further, the anionization treatment of the protein fiber product is performed by impregnating 100% by weight of the protein fiber product with a glue mainly containing sulfamic acid, followed by drying and curing.

[0003]

However, among the treating agents for preventing yellowing of conventional protein fiber products and for preventing the strength and elongation from being reduced, those containing dicarboxylic acid as a main component are p-type compounds.
H is a strong acid of 1.4 to 2.0, so that the protein fiber is greatly damaged and the dyeing of the anionic dye on the protein fiber is accelerated, resulting in uneven dyeing. There is a concern that the processed product may affect human health. In addition, protein fiber products treated with conventional shrink-prevention / wrinkle-preventing agents have a hardened feel, cannot control the hygral expansion behavior, and are also concerned about the effect on human health. Further, when the treatment is carried out using a conventional leveling agent, the adsorption rate of the dye is not improved, and the dye reproducibility is poor. Further, in the conventional anionization treatment method, there is a problem that the protein fiber product reacts sensitively to the difference in the temperature distribution during drying, and when the protein fiber product is a fabric, a significant color difference occurs between the ear portion and the central portion.

[0004] A first object of the present invention is to provide a processing method which does not affect human health, prevents yellowing of protein fiber products, and does not reduce the high elongation. Second embodiment of the present invention
It is an object of the present invention to provide a treatment method which has no effect on human health, does not impair the feeling of protein fiber products, controls the hygral expansion behavior, and improves dimensional stability. A third object of the present invention is to provide a method for treating a protein fiber product which has an improved dye adsorption rate and good dye reproducibility. A fourth object of the present invention is to provide a treatment method in which a difference in temperature distribution during drying does not appear in the treated protein fiber product, and a protein fiber product having a high light fastness and a beautiful color can be obtained.

[0005]

The invention according to claim 1 is
A colorless anion-activating substance in which two or three reactive groups having one or both of a substitution function and an addition function capable of reacting with a protein fiber product and an anion-active group are linked by a molecular base of an aryl group is used. PH containing 0.05 to 50% by weight.
After preparing a treatment aqueous solution of 0 to 9.5 and bringing the protein fiber product into contact with the treatment aqueous solution, the protein fiber product in contact with the treatment aqueous solution in liquid, in the air or in steam is prepared for 30 to 30 minutes.
This is a method for treating a protein fiber product which is treated at a temperature of 135 ° C. for 1 to 200 minutes. By treating the protein fiber product with the treatment aqueous solution under the above conditions, one or more reactive groups selected from amino group, lysine group, arginine group, histidine group and thiol group possessed by the protein fiber product and anion activation Cross-linking is mainly performed between the reactive groups of the substance and partial graft polymerization, and the above object is achieved. That is, in general, protein fibers are boiled, and the cysteine group (SH group) of the side chain reacts with the cystine bond (-SS-) by boiling, thereby breaking the cystine bond and loosening the polypeptide orientation of the protein fiber. Although the reaction is easily prevented, the anion activator prevents the reaction, thereby improving the dimensional stability of the protein fiber product and effectively acting on the behavior control of the hygral expansion. In addition, damage to the polypeptide bonds of the protein fibers is suppressed, and yellowing and a decrease in high elongation of the protein fiber products due to high temperature and high pressure are prevented.

Further, when the protein fiber product is treated with the treatment aqueous solution under the conditions described in claims 8, 9, 11, and 12,
When the amount of the colorless anion activator used is reduced to about 0.1 to 2.0% by weight, a part of the amino groups of the protein fiber is blocked by crosslinking. By this blocking, the amino group of the protein fiber is anionized, and the dyeing speed of the acid dye, the 1: 2 metal-containing dye or the reactive dye for dyeing the protein fiber is suppressed, and the dyeing is slowed, thereby enabling uniform dyeing. In addition, the above-described blockade activates the amino group of the protein fiber by anion activation, thereby enabling cation staining.

In particular, when the treatment aqueous solution contains sodium sulfate, sodium carbonate, cerium (IV) ammonium nitrate or cerium (IV) ammonium sulfate, cerium (IV) ammonium nitrate or cerium (IV) sulfate ) Ammonium acts as a cross-linking initiator for protein fibers, sodium sulfate acts as an adsorbent for colorless anion activators, and sodium carbonate acts as a fixative for it. Claim 1 further comprises an anion activating substance.
The divinyl monomer or the trivinyl monomer according to claim 3, wherein the treatment aqueous solution according to claim 10 is cerium.
When (IV) ions are contained, graft polymerization occurs in the protein fiber product and a cross-linking reaction occurs to improve the dimensional stability of the protein fiber product.

[0008]

Next, an embodiment of the present invention will be described. The protein fibers constituting the protein fiber product of the present invention are animal hair fibers such as wool, cashmere, alpaca, angora and mohair, or silk fibers obtained from cocoons such as silkworms and wild silkworms. Protein fiber products include rose hair, top, yarn, woven fabric, knitted fabric, non-woven fabric and the like made from these fibers.
The protein fiber product of the present invention contains at least 10% by weight of protein fiber. The treatment aqueous solution of the present invention is a colorless color having two or three reactive groups having one or both of a substitution function and an addition function capable of reacting with a protein fiber product and an anion active group linked by an aryl group molecular base. Is an aqueous solution containing 0.05 to 50% by weight of an anion activator of pH 3.0 to 9.5. If the number of the above-mentioned reactive groups is less than 2 or the content is less than 0.05% by weight, the object of the present invention is not attained. Do not achieve. In particular, when the content exceeds 30% by weight, in terms of a bath ratio, an unfixed colorless anion activator flows out into the waste liquid, resulting in a loss.

[0009] In addition to the above colorless anion activator, a treatment aqueous solution may be prepared by further containing a colorless reactive dye for dyeing cellulose or a colorless reactive dye for dyeing protein fibers. In the present specification, the colorless anion activator and the colorless dye are a colorless anion activator and a dye having no chromophore, even in a solid before dissolution of water, and even after dissolution in water. Means Examples of colorless reactive dyes for dyeing cellulose fibers include trichloropyrimidines such as Cibacron T and Drimarene X, two fluorotriazines (bifunctional dyes) such as Cibacron LS, monochlorotriazines such as Sumifix H, and Sumifix Supra dyes. Such as monochlorotriazines, bifunctional dyes of β-sulfatoethylene, monofluorotriazines such as Cibacron F, Remazo
Β-sulfatoethylene sulfone, such as Levafix
Dichloroquinoxaline such as E dye, Lavafix EA,
Difluoro-monochloropyrimidine such as Drimarene K dye, dichlorotriazine such as Procion MX, Ka
and mononicotinic acid triazine dyes such as yacelonreact dyes. Colorless reactive dyes for dyeing protein fibers include dyes having two bromoacrylamide groups as reactive groups, such as Lanasol dyes.

The reactive group having a colorless anion activator capable of reacting with the above-mentioned protein fiber product has a dichlorotriazinyl group, a trichloropyrimidinyl group, a chlorodifluoropyrimidinyl group, a dichloropyrimidinyl group,
Examples thereof include a dichloropyridazinyl group, a dichloroquinoxalinyl group, and a dichlorophthalazinyl group. In addition, a monofluorotriazine group is given as one reactive group having a substitution function of the anion activator, and a vinyl sulfone group is given as one reactive group having an additional function of this anion activator. Further, as a reactive group having two substitution functions of the anion activator, a bromoacrylamide group can be mentioned. These reactive groups are selected because they react easily and strongly with amino groups in the main chain of protein fibers, cysteine groups (SH groups), lysine groups, and the like in the side chains.

As an example, the anion-active group of the colorless anion activator is a sulfone group (Claim 5), the molecular base of the aryl group is benzene (Claim 6), and has two substitution functions. When the reactive group is a dichlorotriazine group (claim 2), the main chain of the protein fiber is an amino group at the position of both chlorines and the side chain is a cysteine group as shown in the following formula (1). , The nucleophilic substitution reaction proceeds effectively and quickly between the two with a high probability.
These crosslinks are covalent and therefore robust,
Crosslinking of a dense network structure occurs. A similar reaction occurs even when the anion active group of the colorless anion activator is a carboxyl group other than a sulfone group, a phosphate group or a sulfate group.

[0012]

Embedded image

As an example of the above-mentioned colorless anion activator, sodium 2,4-dichloro-s-triazin-6-yl-p-aminosalicylate (2,4-dichloro-s
-triazine-6-yl-p-aminosalicylic acid sodium sal
t), 2,4-dichloro-s-triazin-6-yl-
m-aminophenylphosphonic acid sodium salt (2,4-dich
loro-s-triazine-6-yl-m-aminophenylphosphonic acid
sodium salt), 2,4-dichloro-s-triazine-
6-yl-aniline (2,4-dichloro-s-triazin-6-yl-an
iline), 2,4-dichloro-s-triazin-6-yl-pn-butyl-aniline (2,4-dichloro-s-triaz)
ine-6-yl-pn-butyl aniline), 2,4-dichloro-s
-Triazin-6-yl- (1-naphthylamine) (2,
4-dichloro-s-triazine-6-yl- (1-naphthylamine)), dichlorotriazinylsulfanilic acid sodium salt (dich
lorotriazinylsulfanilic acid sodium salt, dichlorotriazinylmethanilic acid sodium salt (dichlorotria
zinylmetanilic acid sodium salt), (1,3,5-
Triacryloylhexahydro-es-triazine) triacrylformal ((1,3,5-triacryloylhexahydro-
s-triazine) triacrylformal), 1,3,5-tris-
(2-methylacryloyl) -hexahydro-s-triazine (1,3,5-tris- (2-methylacryloyl) -hexahydro-s-
triazine), 1,3,5-tris- (2-methylacryloyl) -hexahydro-s-triazine (1,3,5-tris)
-(2-ethylacryloyl) -hexahydro-s-triazine), 1,
3,5-tris- (2-propylacryloyl) -hexahydro-s-triazine (1,3,5-tris- (2-propylacry
loyl) -hexahydro-s-triazine), 1,3,5-tris-
(2-isopropylacryloyl) -hexahydro-es-triazine (1,3,5-tris- (2-isopropylacryloyl) -h
exahydro-s-triazine), 1,3,5-tris- (2-
Butylacryloyl) -hexahydro-s-triazine (1,3,5-tris- (2-buthylacryloyl) -hexahydro-s-triazi
ne), 1,3,5-tris- (2-isobutylacryloyl) -hexahydro-s-triazine (1,3,5-tris-
(2-isobuthylacryloyl) -hexahydro-s-triazine), 1-
Acryloyl-3,5-bis- (2-ethylacryloyl) -hexahydro-s-triazine (1-acryloyl-3,5
-bis- (2-ethylacryloyl) -hexahydro-s-triazine), 1
-(2-butylacryloyl) -3,5-bis- (2-
Ethylacryloyl) -hexahydro-es-triazine (1- (2-buthylacryloyl) -3,5-bis- (2-ethylacryloyl)
-hexahydro-s-triazine), 2,4-dichloro-6-
(O-chloroanilino) -1,3,5-triazine (2,
4-dichloro-6- (o-chloroanilino) -1,3,5-triazine),
2,4-dichloro-4-hydroxy-1,3,5-triazine (2,4-dichloro-4-hydroxy-1,3,5-triazine),
Triacryloyl-hexahydro-1,3,5-triazine and 1
-Ethoxy-4- (dichloro-1,3,5-triazinyl) -naphthalene (1-ethoxy-4- (dichloro-1,3,5-triaz
inyl) naphthalene), triaryl cyanurate (triall)
yl cyanurate), triaryl isocyanurate (triall
yl isocyanurate), trimethallyl isocyanurate (tri
methallyl isocyanurate), microbutanyl (2-p
-Chlorophenyl-2- (1h-1,2,4-triazol-1-yl-methyl)) (microbuthanyl (2-p-chloroph
enyl-2- (1h-1,2,4-triazol-1-yl-methyl)))), N, N '
-Methylenebisacrylamide, divinyl adipate,
Divinylbenzene and 3,5,9 divinyl-2,4
At least one divinyl monomer selected from the group consisting of 8,10-tetraoxaspiro [5,5] undecane, or 1,3,5-triacryloylhexahydro-s-triazine, 1,2,4-triazine Examples include vinylcyclohexane, triallyl trimellitate, and triallyl isocyanurate.

The above-mentioned triazines include low polymers such as monomers, dimers and trimers. Among them, monomeric triazine is preferable because it has a small molecular weight, easily reacts with a reactive group of a protein fiber, and easily forms a network structure by crosslinking. When adding the above compound to the dyeing liquor, the above compound is dissolved or dispersed in water in advance, or dissolved in water-soluble alcohols, acetone, xylene, toluene, benzene or dioxane, and then the emulsifier ( It is preferable to mix with water using an emulsifier. Further, the p of the treatment aqueous solution of the present invention
H is adjusted to the range of 5 to 9.5 by adding an acid such as acetic acid, formic acid, phosphoric acid or the like, or an alkali such as sodium sulfate, sodium carbonate or sodium hydroxide as an auxiliary agent.

Further, the processing method of the present invention includes the following six types. The first method is an immersion method in which a treatment aqueous solution is stored in a liquid tank, and a protein fiber product is immersed in the liquid tank and treated at a predetermined temperature and time in the treatment aqueous solution. The second method is a method in which a protein fiber product is filled in a treatment tank and fixed, and a treatment aqueous solution is circulated and supplied into the tank. This method is suitable when the protein fiber product is rose hair, top or yarn. First and second
In the method, the protein fiber product is treated in a treatment aqueous solution.
A third method is to store the treatment aqueous solution in a padding tank, immerse the protein fiber product in this tank, and simultaneously pad (drain) the protein fiber product, pre-dry the protein fiber product, and cure the protein fiber product at a high temperature. Dry cure (Pad-Dry-
Cure) method. In a third method, the protein fiber product is treated in air. The fourth method is to store a treatment aqueous solution in a padding tank, immerse the protein fiber product in this tank, and simultaneously perform padding (liquid removal), and then inject steam into the protein fiber product (Pad-Steam). Is the law. This method includes a method of injecting steam at a high pressure (0.2 to 0.3 MPa), a method of injecting steam at a normal pressure (0.1 MPa),
There is a method of spraying at a high temperature (80 to 100 ° C.). Fifth
The method of the above is to prepare a printing paste by mixing the treatment aqueous solution with the paste,
This is a printing method in which after printing on the surface of a protein fiber product, steaming is applied for treatment. The sixth method is a spray method in which a treatment aqueous solution is sprayed onto the surface of a protein fiber product by a spray nozzle, and then steaming is applied for treatment. In the fourth to sixth methods, the protein fiber product is treated in steam. In addition, the first
In the sixth to sixth methods, when the protein fiber product is a dyed product, the treatment of the protein fiber product is performed before or after the dyeing.

The processing conditions of the present invention include the following five types according to the processing purpose. The first treatment condition is the condition according to claim 8, wherein the content of the colorless anion activator is 0.1 to 30% by weight, preferably 5 to 15% by weight of the protein fiber product. 70 protein fiber products in contact with the aqueous solution
To 135 ° C., preferably 110 to 125 ° C.
The treatment is carried out for up to 120 minutes, preferably for 10 to 30 minutes. When the protein fiber product is further set with high-temperature / high-pressure water or steam after being treated under these conditions, or is treated in a plasma state, yellowing of the product is prevented and the high elongation is not reduced. The second treatment condition is the condition according to claim 9, wherein the content of the colorless anion activator is 0.1 to 30% by weight of the protein fiber product, preferably 5 to 1%.
5% by weight of the protein fiber product in contact with the treatment aqueous solution at a temperature of 30 to 100 ° C, preferably 90 to 100 ° C.
The treatment is carried out for up to 60 minutes, preferably for 5 to 30 minutes.
The third processing condition is the condition described in claim 10, and further restricts the second processing condition. That is, in addition to the colorless anion activator, sodium sulfate is further added in an amount of 3 to 100 g, preferably 10 to 1 liter of the liquor.
~ 50 g, 1 liter of sodium carbonate per liter of dyeing liquor
-20 g, preferably 2-5 g, of cerium (IV) ammonium nitrate or cerium (IV) ammonium sulfate in an amount of 0.1 to 10% by weight, preferably 1.0 to 3.0% by weight of the protein fiber product.
% By weight to prepare a treatment aqueous solution, and the protein fiber product contacted with the treatment aqueous solution is heated to 30 to 100 ° C., preferably 40 to 100 ° C.
The treatment is performed at a temperature of ６０60 ° C. for 1 to 60 minutes, preferably 40 to 60 minutes. Sodium sulfate adsorbs the colorless anion activator on the protein fiber, and sodium carbonate is added to fix it. The addition of cerium ammonium nitrate or cerium ammonium sulfate causes Ce ⁴⁺ ions to be graft-copolymerized to protein fibers in a treatment aqueous solution and, at the same time, to be cross-linked to protein fibers. That is, when treated under the second and third conditions, the feeling of the protein fiber product is not impaired, the shrinkage / wrinkle resistance of the protein fiber product is improved, and the dimensional stability is improved by controlling the hygral expansion behavior. be able to.

The fourth treatment condition is the condition according to claim 11, wherein the content of the colorless anion activator is 0.05 to 20% by weight, preferably 0.05 to 20% by weight of the protein fiber product.
2.0% by weight, and treats the protein fiber product in contact with the treatment aqueous solution at a temperature of 80 to 100 ° C for 20 to 200 minutes, preferably 10 to 60 minutes. As a specific example, 0.05 to 20% by weight of (1,3,5-triacryloylhexahydro-es-triazine) triacrylformal is added to a protein fiber product, and a reactive dye (Lanaso
l 3G) is immersed in a 50 ° C. aqueous solution containing 1.0% by weight of a penetrant and 0.1% by weight of a penetrant, heated to 100 ° C. in 40 minutes, and held there for 30 minutes. And conditions for slow cooling and washing with water. When treated under these conditions, rapid adsorption of the dye to the protein fiber product is suppressed, the dyeing rate is improved, and the dye reproducibility is improved. Particularly when the protein fiber product is a fabric, uniform dyeing can be performed. The fifth treatment condition is the condition according to claim 12, wherein the content of the colorless anion activator is 0.1 to 30% by weight, preferably 10 to 30% by weight of the protein fiber product.
% Of the protein fiber product in contact with the aqueous solution.
0 to 100 ° C, preferably at a temperature of 90 to 100 ° C.
The treatment is performed for 200 minutes, preferably 10 to 60 minutes. As an example of this, for protein fiber products (1,
The protein fiber product is immersed in a treatment aqueous solution containing 0.1 to 20% by weight of 3,5-triacryloylhexahydro-es-triazine) triacrylformal at 25 ° C.
In 50 minutes, the temperature is raised to 50-100 ° C.
After holding for 0 minutes, slowly cooling, and washing with water, the following conditions can be mentioned.
When treated under these conditions, the protein fiber product is anionized, so that a difference in temperature distribution during drying does not appear in the treated protein fiber product, and color unevenness does not occur. Also, it is possible to realize a beautiful and high-fast dyeing by a cationic dye. Furthermore, cross-linking is carried out by a strong covalent bond between the amino group of the main chain of the protein fiber, the cysteine group of the side chain, etc. and the two or three reactive groups of the colorless anion activator. Therefore, when the protein fiber product is a fabric, the shrink resistance and wrinkle resistance can be improved by 30% or more as compared with the untreated one.

[0018]

Next, examples of the present invention will be described together with comparative examples. <Example 1> A plain woven fabric woven from a 2/60 warp yarn of 100% polyester and a 1/60 weft yarn of 100% wool was prepared. After removing the fluff on the surface of the woven fabric in the baking process, dirt and the like of the woven fabric were removed in the scouring process. Next, a disperse dye or the like was prepared based on the weight of the woven fabric according to the following first formulation to prepare a dyeing solution having a pH of 5.5. The woven fabric was dyed in gray with this dyeing solution using a jet dyeing machine. That is, the above-mentioned woven fabric was put into a dyeing machine, heated to 120 ° C., held there for 20 minutes, cooled slowly, washed with water and dried.

(First Formulation) CI Disperse Blue 56 0.6% by weight CI Disperse Red 60 0.2% by weight CI Disperse Yellow 64 0.4% by weight CI Acid Black 58 0.25% by weight Acetic acid (99%) 0.5% by weight Elaster TS (Ssangyong, carrier) 2.0% by weight 2,4-dichloro-6- (o-chloroanilino) -1,3,5-triazine (colorless anion activator: Sandospace R) 5.0% by weight A treated aqueous solution of the following second formulation was prepared, which was the same as the first formulation, except that the dyed finished fabric was not added with a dye. The woven fabric is put into the same dyeing machine with the treatment aqueous solution,
The temperature was raised to 20 ° C., kept there for 20 minutes, cooled slowly, washed with water and dried.

(Second formulation) Acetic acid (99%) 0.5% by weight Elaster TS (Ssangyong, carrier) 2.0% by weight 2,4-dichloro-6- (o-chloroanilino) -1,3, 5-triazine (colorless anion activator: Sandospace R) 5.0% by weight <Comparative Example 1> Except that colorless anion activator (Sandospace R) was not added in each of the first and second formulations.
The same plain woven fabric as in Example 1 was treated in the same manner as in Example 1.

<Comparative Example 2> In the first and second formulations, instead of the colorless anion activator (Sandospace R), a treatment agent containing formalin as a main agent (trade name: Irgasol HTW, Ciba)
The same plain woven fabric as in Example 1 was treated in the same manner as in Example 1, except that 3.0% by weight was added to the weight of the fabric. <Comparative Example 3> In place of the colorless anion activator (Sandospace R) in the first and second formulations, a treating agent mainly containing dicarboxylic acid (trade name: Basolan 2454, manufactured by BASF) was added to the weight of the fabric. On the other hand, except that 3.0% by weight of each was added.
The same plain woven fabric as in Example 1 was treated in the same manner as in Example 1. <Comparative Example 4> In place of the colorless anion activator (Sandospace R) in the first and second formulations, a dicarboxylic acid was used in the same manner as a treating agent mainly containing dicarboxylic acid (trade name: Basolan 2454, manufactured by BASF). Treatment agent as main agent (trade name: Scale Se
t AC, manufactured by Senka Kogyo) was added in the same manner as in Example 1 except that 3.0% by weight was added to the weight of the textile, and the same plain woven fabric as in Example 1 was treated.

<Comparative Evaluation 1> (a) Shrinkage and tear strength of woven fabric The shrinkage ratio after dyeing of the plain woven fabric dyed in Example 1 and Comparative Examples 1 to 4 after dyeing and the length and width of Tear strength,
In addition, the shrinkage ratio and the tear strength of the warp and weft of the plain woven fabrics subjected to the hot water treatment in Example 1 and Comparative Examples 1 to 4 were measured, respectively, before and after the treatment. Table 1 shows the results.

[0023]

[Table 1]

As is apparent from Table 1, the total shrinkage after dyeing and after hot water treatment exceeds 10% in Comparative Examples 1 to 4, whereas it is less than 10% in Example 1. Especially after hot water treatment, it was extremely small at 5.5%. Further, the fabric treated in Example 1 had higher tear strength than the fabric treated in Comparative Example 1.

(B) Hygral expansion of woven fabric,
Feeling characteristics and yellow index Hygral expansion of plain woven fabric dyed in Example 1 and Comparative Examples 1 to 4, and Example 1 and Comparative Examples 1 to
The Hygral expansion, hand characteristics and yellow index of the plain woven fabric treated with hot water in 4 were measured. Table 2 shows the results. Hygral expansion is available from I.D. W. S. (International Wool Bureau). The hand characteristics are based on the KES hand test, and the tensile (E)
(MT, RT) and shear (G, 2HG5). The yellow index was measured only for the fabric after the hot water treatment based on JIS L1081-D method. A yellow index of 100% is white, and the smaller the ratio is, the more yellow the color is. The yellow index before the hot water treatment was all 79.0%.

[0026]

[Table 2]

As is clear from Table 2, the hygral expansion of the woven fabric was smaller in Example 1 than in Comparative Examples 1 to 4 both after dyeing and after hot water treatment. In addition, the hand properties of the woven fabric of Example 1 were more flexible and superior than those of Comparative Examples 1 to 4. Furthermore, the yellowing degree of the woven fabric is comparative example 1 in Example 1.
Less than four.

<Example 2> A 1/2 twill woven fabric prepared by using 1/40 strongly twisted yarn of 100% wool (1500 times / m Z twist) as the warp yarn and the weft yarn, respectively. This twill fabric was treated in a continuous high-pressure steamer. That is, 6% by weight of the woven fabric is stored in a service tank provided outside the can body.
(1,3,5-triacryloylhexahydro-
A treatment aqueous solution having a pH of 7.0 in which (es-triazine) triacrylformal was dissolved was stored. The service tank was connected to the can body, and the treatment aqueous solution in the tank was supplied to the trough in the can at regular intervals by pressurization. The woven fabric is wound around a roll and set in this aqueous solution, and the pressure in the can is set to 0.
The wet heat setting was performed at 2 MPa and a treatment aqueous solution temperature of 110 ° C. for 5 minutes. After the completion of the moist heat setting, the fabric was dehydrated and dried.

<Comparative Example 5> The same fabric as in Example 5 was set in a treatment aqueous solution containing no (1,3,5-triacryloylhexahydro-es-triazine) triacrylformal in the same manner as in Example 5. Wet heat setting. After the completion of the moist heat setting, the fabric was dehydrated and dried. <Comparative Evaluation 2> Tensile strength and elongation, tear strength, opening angle, shrink resistance (TWSTM31 method), and Hygral expansion of each fabric of Example 2 and Comparative Example 5 were measured. Table 3 shows the results. In the table, Hygral expansion is indicated by HE.

[0030]

[Table 3]

As apparent from Table 3, the woven fabric of Example 2 had a higher elongation and tear strength than the woven fabric of Comparative Example 5, respectively. The opening angle of the woven fabric of Example 2 was larger than that of Comparative Example 5, and the woven fabric was hard to wrinkle. Further, the fabric of Example 2 was smaller than the fabric of Comparative Example 5 in terms of the shrinkage resistance and the hygral expansion of the fabric.

Example 3 A high-density gabardine fabric woven using 100% wool and 2/72 strong twist yarn as warp and weft yarns was prepared. The woven fabric was first subjected to shrink-prevention processing, that is, Kroy-processing. That is, the above-mentioned woven fabric is treated with a solution of DCCA (potassium dichloroisocyanurate) at a concentration of about 6 g / l at a temperature of about 25 ° C. for 30 minutes using a Wins dyeing machine, and then 6 g / l of sodium sulfate and 2 g / l of dicarboxylic acid (Basolan ASB). And the fabric was further treated at about 65 ° C. for about 40 minutes. The Kroy-treated fabric was plain-dyed gray with a treatment solution having a pH of 4.8 and formulated with a third formulation containing the following reactive dye for wool. That is, the above-mentioned woven fabric was put into a dyeing machine, heated to 100 ° C., held there for 30 minutes, gradually cooled, washed with water and dried. The ratio of the dye or the like is a ratio to the weight of the fabric.

(Third formulation) Lanasol Blue 3G 0.5% by weight Lanasol Red 6G 0.2% by weight Lanasol Yellow 4G 0.4% by weight Albegal B 1.0% by weight 2,4-dichloro-6- (o -chloroanilino) -1,3,5-triazine (colorless anion activator: Sandospace R) 3.0% by weight <Comparative Example 6> The same gabardine fabric as in Example 3 was first used in Kr.
oy processed. The Kroy-treated fabric was then plain-dyed in the same manner as in Example 3 with a fourth formulation containing the following reactive dye for wool. After dyeing, it was washed with water and dried. The ratio of the dye or the like is a ratio to the weight of the fabric.

(Fourth Formulation) Lanasol Blue 3G 0.5% by weight Lanasol Red 6G 0.2% by weight Lanasol Yellow 4G 0.4% by weight Albegal A 1.0% by weight Albegal B 2.0% by weight Am-Sulphate 3.0% by weight <Comparative Evaluation 3> Each of the woven fabrics of Example 3 and Comparative Example 6 subjected to the Kroy processing was given a wash and wear property that can be adjusted in form without ironing. In the dyed fabric of Comparative Example 6, the dye did not penetrate into the fabric structure. For this reason, a part (for example, a weaving step) having a different dyeing property due to partial exposure to sunlight in the state of the white cloth before dyeing was dyed differently from other parts, and was not uniform. On the other hand, in the woven fabric dyed in Example 3,
The dye penetrated into the fabric structure. As a result, Comparative Example 6
Even if there is a part of the white fabric before dyeing that is partially exposed to sunlight and has different dyeing properties, this part, like the other parts, is uniformly dyed throughout the fabric, and The clearness was also good.

Example 4 A woven fabric of variable weave was prepared by using 1/16 wool of 100% wool as warp yarn and weft yarn, respectively. Using a rotary screen printing machine, a fine floral pattern was printed on the fabric with a printing paste (viscosity: 1000 cP) having a pH of 5.0 prepared according to the following fifth prescription and dried. Steamed for 30 minutes. After steaming, the fabric was washed with water and dried. The dried fabric was placed in an overflow dyeing machine under normal pressure, and the gray color of the acidic dye and the pink color of the cationic dye were dyed in the same bath according to the following sixth formula. That is, the above woven fabric was put into a dyeing machine, heated to 100 ° C., kept there for 40 minutes, cooled slowly, washed with water and dried. The ratio of the dye or the like is a ratio to the weight of the fabric.

(Fifth Formulation) 2,4-dichloro-6- (o-chloroanilino) -1,3,5-triazine (colorless anion activator: Sandospace R) 10.0% by weight Meypro GUN NP- 8 (8% original glue) 50.0% by weight Irgapadol PN 1.0% by weight Water 39.0% by weight (sixth formulation) CI Acid Black 58 1.0% by weight CI Basic Red 27 0.5% by weight acetic acid (99%) 1.0% by weight Texaton OA (Anti-precipitating agent) 2.0% by weight When treated and dyed according to the method of Example 4, a clear printed product having a gray ground color and a pink flower portion was obtained. Obtained.
In particular, the shape of the print was very sharp.

<Example 5> A yarn in which 100/1 wool 1/80 ultrafine yarn was twisted with 100/1 sea island cotton yarn for the warp yarn and the weft yarn, respectively, was used to obtain a basis weight of about 120 g / m2.
² plain plain fabrics were woven. This ultra-fine wool yarn is obtained by stretching the wool fiber by 40 to 50% in the spinning process and setting the fiber diameter to 10 to 50%.
20% thinner silky glossy softest ultra-fine yarn (manufactured by Nippon Kaori Co., Ltd.), which is very sensitive to high temperature treatment such as dyeing and easy to cause uneven dyeing. It is a yarn that tends to cause a decrease in strength. After carefully scouring the flat fabric while keeping it wide, cotton yarn is applied to a delicate fabric using a very mild liquid dyeing machine (Circular dyeing machine SR type, manufactured by HISAKA MFG.) And wool yarn were dyed in one bath. That is, the woven fabric was put into the above-mentioned dyeing machine, and water was stored so as to have a bath ratio of 1: 8 (fabric: water).
The mixture was added at a rate of 1 and heated to 40 ° C. and kept for 5 minutes.

(Seventh Formulation) Triacryloyl-hexahydro-1,3,5-triazine 3.0% by weight Cibacron Scarlet LS-2G 2.5% by weight Cibacron Red LS-B 0.5% by weight Lanasol Red 2G 2. 0% by weight Triacryloyl-hexahydro-1,3,5 triazine which is a colorless anion activator is further added to the above solution.
0% by weight was added, and after 5 minutes, the above-mentioned wool dye and cotton dye were sufficiently dissolved and added together. After adding the dye, the dye is diffused sufficiently uniformly on the fabric for 10 minutes, and then heated to 100 ° C. at a rate of 1.0 ° C./min.
Boiling continued for 0 minutes. After further cooling to 70 ° C. for 10 minutes, sodium sulfate was added at a rate of 20 g / l, kept for 20 minutes, cooled to 60 ° C., and soda ash was added at a rate of 10 g / l and dyed for 30 minutes. The dye on the cotton side was fixed. Thereafter, it was washed with water and subsequently washed with hot water at 80 ° C. for 5 minutes to remove unfixed dye, thereby completing dyeing. This dyeing gave the plain fabric a very bright red color of the same color for both cotton and wool.

Comparative Example 7 The procedure of Example 5 was repeated except that triacryloyl-hexahydro-1,3,5 triazine, a colorless anion activator, was not added.
The same plain woven fabric was dyed. <Comparative Evaluation 4> The dyeing fastness and tear strength of each of the fabrics of Example 5 and Comparative Example 7 were measured, and the same color of cotton and wool constituting the fabric was visually evaluated. Table 4 shows the results.

[0040]

[Table 4]

As is clear from Table 4, among the dyeing fastnesses of the woven fabric, the light fastness and the washing fastness were the same as those of Example 5 and Comparative Example 7.
However, the woven fabric of Example 5 was superior to the rub fastness and tear strength of Comparative Example 7 in wet rub fastness and tear strength. In addition, when compared visually, the woven fabric of Comparative Example 7 had a light color and wool was dark and had a heather tone, and had a feeling of irritability, whereas the woven fabric of Example 5 had the same color as cotton and wool. There was no unevenness in dyeing and there was color.

[0042]

As described above, according to the treatment method of the present invention, since no formalin is used, there is no effect on human health, yellowing of protein fiber products is prevented, and high elongation is reduced. I will not let you. According to another treatment method of the present invention, since no formalin is used, there is no effect on human health, the feeling of protein fiber products is not impaired, and the hygral expansion behavior is controlled to improve dimensional stability. According to still another treatment method of the present invention, the amino group of the protein fiber is blocked by the anion activating substance, and the dye is dyed by competing with the anionic dye of the protein fiber due to the anionic property of the anion activating substance. And dyes uniformly. In particular, in a product in which protein fibers and cellulose fibers are mixed, some of the OH groups of the cellulose fibers are also blocked by the anion activator, and the protein fibers and the cellulose fibers are dyed in the same color, and a reduction in strength is prevented. Works.

Claims (14)

[Claims] 1. A colorless anionic active in which two to three reactive groups having one or both of a substitution function and an addition function capable of reacting with a protein fiber and an anionic active group are linked by a molecular base of an aryl group. After contacting a protein aqueous solution with a treatment aqueous solution having a pH of 3.0 to 9.5 containing 0.05 to 50% by weight of a chemical substance, the protein fiber product is subjected to 30 to 135 in the treatment aqueous solution, in the air or in steam. A method for treating a protein fiber product, wherein the treatment is performed at a temperature of 1 to 200 minutes. 2. The reactive group having a substitution function of the anion activator is a dichlorotriazinyl group, trichloropyrimidinyl group, chlorodifluoropyrimidinyl group, dichloropyrimidinyl group, dichloropyridazinyl group, dichloroquinoxalinyl group or 2. The treatment method according to claim 1, which is a dichlorophthalazinyl group. 3. The reactive group having one substitution function of the anion activator is a monofluorotriazine group, and the reactive group having one additional function of the anion activator is a vinyl sulfone group. 1. The processing method according to 1. 4. The treatment method according to claim 1, wherein the reactive group having two substitution functions of the anion activator is a bromoacrylamide group. 5. The treatment method according to claim 1, wherein the anion-active group of the anion-activating substance is a sulfone group, a carboxyl group, a phosphate group or a sulfate group. 6. The processing method according to claim 1, wherein the molecular base of the aryl group has a molecular structure derived from benzene, naphthalene, anthracene, phenanthrene, or diphenyl. 7. The process aqueous solution according to claim 1, wherein the treatment aqueous solution further contains a colorless reactive dye for cellulose fiber dyeing or a colorless reactive dye for protein fiber dyeing in an amount of 0.1 to 30% by weight of the protein fiber product. Processing method. 8. The treatment aqueous solution contains an anion activator in an amount of 0.1 to 30% by weight of the protein fiber product, and the protein fiber product in contact with the treatment aqueous solution is heated at a temperature of 70 to 135 ° C. for 10 to 10%.
The processing method according to any one of claims 1 to 7, wherein the processing is performed for 120 minutes. 9. The treatment aqueous solution contains an anion activator in an amount of 0.1 to 30% by weight of the protein fiber product, and the protein fiber product in contact with the treatment aqueous solution is treated at a temperature of 30 to 100 ° C. for 1 to 6%.
The processing method according to any one of claims 1 to 7, wherein the processing is performed for 0 minutes. 10. The treatment aqueous solution further contains sodium sulfate in an amount of 3 to 100 g per liter of the treatment aqueous solution and sodium carbonate in an amount of 1 to 20 g per liter of the treatment aqueous solution.
g, cerium (IV) ammonium nitrate or cerium sulfate (I
V) 0.1 to 10% by weight of the protein fiber product of ammonium, and 30 to 1% of the protein fiber product in contact with the treatment aqueous solution.
The treatment method according to claim 9, wherein the treatment is performed at a temperature of 00C for 1 to 60 minutes. 11. The treatment aqueous solution contains an anion activator in an amount of 0.05 to 20% by weight of the protein fiber product, and the protein fiber product contacted with the treatment aqueous solution is treated at a temperature of 80 to 100.degree.
The processing method according to any one of claims 1 to 7, wherein the processing is performed for 0 to 200 minutes. 12. The treatment aqueous solution contains an anion activator in an amount of 0.1 to 30% by weight of the protein fiber product, and the protein fiber product in contact with the treatment aqueous solution is heated at a temperature of 50 to 100 ° C. for 5 to 100 ° C.
The processing method according to any one of claims 1 to 7, wherein the processing is performed for 200 minutes. 13. The colorless anion activator comprises 2,4
-Dichloro-s-triazin-6-yl-p-aminosalicylic acid sodium salt, 2,4-dichloro-s-triazin-6-yl-m-aminophenylphosphonic acid sodium salt, 2,4-dichloro-s- Triazin-6-yl-aniline, 2,4-dichloro-s-triazine-6
Yl-pn-butyl-aniline, 2,4-dichloro-
s-triazin-6-yl- (1-naphthylamine),
Dichlorotriazinylsulfanilic acid sodium salt, dichlorotriazinylmethanilic acid sodium salt, (1,
3,5-triacryloylhexahydro-es-triazine) triacrylformal, 1,3,5-tris-
(2-methylacryloyl) -hexahydro-s-triazine, 1,3,5-tris- (2-methylacryloyl) -hexahydro-es-triazine, 1,3,5-
Tris- (2-propylacryloyl) -hexahydro-es-triazine, 1,3,5-tris- (2-isopropylacryloyl) -hexahydro-s-triazine, 1,3,5-tris- (2-butylacryloyl)
-Hexahydro-s-triazine, 1,3,5-tris- (2-isobutylacryloyl) -hexahydro-s
-Triazine, 1-acryloyl-3,5-bis- (2
-Ethylacryloyl) -hexahydro-s-triazine, 1- (2-butylacryloyl) -3,5-bis-
(2-ethylacryloyl) -hexahydro-es-triazine, 2,4-dichloro-6- (o-chloroanilino) -1,3,5-triazine, 2,4-dichloro-4
-Hydroxy-1,3,5-triazine, triacryloyl-hexahydro-1,3,5-triazine and 1-
Ethoxy-4- (dichloro-1,3,5-triazinyl) -naphthalene, triaryl cyanurate, triaryl isocyanurate, trimethallyl isocyanurate, microbutanyl (2-p-chlorophenyl-2- (1h-
The process according to any one of claims 1 to 12, comprising at least one kind of 1,2,4-triazol-1-yl-methyl)). 14. A colorless anion activator comprising N,
N'-methylenebisacrylamide, divinyl adipate, divinylbenzene, and 3,5,9 divinyl-2,
At least one divinyl monomer selected from the group consisting of 4,8,10-tetraoxaspiro [5,5] undecane, or 1,3,5-triacryloylhexahydro-s-triazine, 1,2,4 At least one selected from the group consisting of trivinylcyclohexane, triallyl trimellitate, and triallyl isocyanurate
The treatment method according to any one of claims 1 to 12, which is a kind of trivinyl monomer.