WO1995016815A1

WO1995016815A1 - Dye fixing agent

Info

Publication number: WO1995016815A1
Application number: PCT/JP1993/001829
Authority: WO
Inventors: Yasuharu Mori; Nobuhiko Ueno; Kouji Midori; Juji Uchida; Masayuki Maeno
Original assignee: Nicca Chemical Co., Ltd.
Priority date: 1992-06-17
Filing date: 1993-12-16
Publication date: 1995-06-22

Abstract

A dye fixing agent for cellulosic fibers dyed with reactive dyes, which comprises a homopolymer comprising vinylamine structural units, a copolymer composed of 5-90 wt.% of vinylamine structural units and 5-90 wt.% of diallylamine structural units, a copolymer composed of 5-90 wt.% of vinylamine structural units and 5-90 wt.% of structural units of a vinylic compound copolymerizable with vinylamine, or a copolymer composed of 5-90 wt.% of vinylamine structural units, 5-90 wt.% of diallylamine structural units and 5-90 wt.% of structural units of a vinylic compound copolymerizable with vinylamine and diallylamine, and/or salts thereof.

Description

Textile dye fixing agent Technical field

The present invention relates to a reactive dye fixative. In particular, the present invention relates to a dye fixing agent which improves the fastness to chlorine of a dyed product dyed with a reactive dye and improves the fastness to moisture. Background art

Reactive dyes are widely used for dyeing cellulosic fibers because of their clear hue and good wet fastness. Also, various dye fixing agents for reactive dyes have been developed to improve the wet fastness. On the other hand, a major drawback of reactive dyes is that the dyes are oxidized and discolored by the chlorine contained in tap water and bleach, and as a countermeasure, dye fixatives that have the property of improving chlorine fastness, etc. Is being developed.

For example, a homopolymer of a monoallylamine derivative (Japanese Patent Application Laid-Open No. 58-31185), a copolymer of a monoallylamine derivative and a diarylamine derivative (Japanese Patent Application Laid-Open No. And a copolymer of an acrylamide derivative containing a tertiary amino group and a diarylamine derivative (Japanese Patent Application Laid-Open No. 1-272887).

However, although the above-mentioned arylamine dye fixatives have a considerable effect, the demand for improving the chlorine fastness in the market is becoming higher, and from the practical point of view of cellulose fibers, If so, no satisfactory effect has yet been obtained. Heat treatment when applying these arylamine-based dye fixatives to printed fabrics. During treatment, yellowing due to the dye fixing agent may be observed in the white area, which may be a problem. Furthermore, with regard to the yellow kiss blue dye, which is frequently used as a light color, the effect of improving the color fastness is not recognized with an arylamine-based dye fixing agent, and improvement is desired. Disclosure of the invention

Accordingly, an object of the present invention is to solve the above-mentioned problems and to provide a dye fixing agent capable of improving the chlorine fastness and wet fastness of a dyed product dyed with a reactive dye. .

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have used a homopolymer or copolymer having a vinylamine structure, which has not been used as a dye fixing agent, and / or a salt thereof. The present inventors have found that the post-treatment of a dyed cellulosic textile dyed with a reactive dye significantly improves chlorine fastness and wet fastness. The present invention has been achieved.

According to the present invention, therefore, there is provided a dye fixing agent used for a cellulosic fiber dyed with a reactive dye, which comprises a vinylamine structural unit represented by the following general formula (I): A vinylamine structural unit comprising a vinylamine structural unit represented by the following general formula (I) and / or a diarylamine structural unit represented by the following general formula (II): A copolymer having 5 to 90% by weight of the unit and 5 to 90% by weight of the diallylamine structural unit, or Z or a salt thereof, or represented by the following general formula (I). A vinylamine structural unit and a vinyl-based compound copolymerizable with the vinylamine, wherein the vinylamine structural unit is 5 to 90% by weight, and the vinyl-based compound structural unit is Is 5 9 0 double % Of a copolymer and / or a salt thereof, a structural unit of vinylamine represented by the following general formula (I), a structural unit of diarylamine represented by the following general formula (II), and A vinyl-based compound copolymerizable with vinylamine and diallylamin, wherein the structural unit of the vinylamine salt is 5 to 90% by weight; A dye fixing agent comprising a copolymer having 5 to 90% by weight of a structural unit and 5 to 90% by weight of the vinyl-based compound and Z or a salt thereof is provided.

One CH ₂ -CH— (I)

NH ₂ CH CH-CH— CH _2- (II)

C H 2 then H 2

Wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. BEST MODE FOR CARRYING OUT THE INVENTION

When the structural unit of the general formula (I) is in a salt form, it can be converted into a salt with an acid such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, sulfamic acid, methanesulfonic acid, and the like. It may be in the form of a salt formed.

—Specific examples of the diarylamine that forms the structural unit of the general formula (II) are diarylamine, which is a secondary amine, methyldiarylamine, and ethyldiamine, which is a tertiary amine. There are liramin and the like. When the structural unit of the general formula (II) is in the form of a salt, it may be in the form of an acid such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, sulfamic acid, methanesulfonate, etc. The salt may be in the form of an amine salt. Ma When R is alkyl, a quaternizing agent such as alkyl halide (alkyl having 1 to 4 carbon atoms), benzyl halide or dialkyl (alkyl having 1 to 2 carbon atoms) sulfuric acid is used. A quaternary ammonium salt may be formed between them.

Vinyl compounds that can be copolymerized with the above-mentioned vinylamine and diarylamine include N-vinylformamide, N-vinylacetamide, and N-vinylpropionic acid amide. — Vinyl amide, styrene, N—methylol acrylamide, N—methylarylamine. N—ethylarylamine, N—propylarylamine, N, N—dimethylarylamine N, N, N—Jetylarylamine, (meta) acrylonitrile, (meta) acrylamide, N—Substituted (meta) acrylamide, (meta) acryl Non-ionic monomers such as vinyl esters, vinyl esters, vinyl ethers, vinyl alcohol, and aryl ethers, (meth) acrylic acid,, unsaturated dicarboxylic acids, and sulfoalkyl (Meth) acrylamide, sulfoalkyl (meth) acrylate, anionic monomer such as (meth) arylsulfonic acid, dialkylaminoalkyl (meth) acrylate, dialkylamine Examples include alkyl (meth) acrylamide and arylamine.

The polymer forming the dye fixing agent of the present invention is, for example, the following general formula (111):

CH ₂ = CH (III)

N H C 0 R

(Wherein, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) N-vinylamide or a derivative thereof is (co) polymerized, and then the obtained polymer is partially hydrolyzed. It is obtained by doing so.

Either radical polymerization or ionic polymerization may be used as the polymerization method, but radical polymerization is preferred because the molecular weight can be easily controlled. Is preferred. As a polymerization initiator for radical polymerization, any of the usual general initiators can be used, but in order to obtain a polymer with a high yield, an azo compound is preferable. Particularly preferred initiators are the hydrochlorides and acetates of 2,2'-azobis-41-amidinopropane, the sodium salts of 4,4'-azobis-4-cyanovaleric acid, the azobis-N, N 'dimethylene butylamidine hydrochloride and sulfate. The amount of these polymerization initiators to be used is usually 0.01 to 1% by weight based on the monomers.

As the polymerization method, known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used. The polymerization reaction is generally carried out at a temperature of usually 3 0~ 1 0 0 ^e C in an inert gas stream. Examples of the solution polymerization method include a method of polymerizing with an aqueous solution having a monomer concentration of 5 to 60% by weight. Examples of the suspension polymerization method include a method of polymerizing an aqueous solution having a monomer concentration of 20 to 80% by weight in a water-in-oil type dispersion state using a hydrophobic solvent and a dispersion stabilizer. Examples of the method include a method in which an aqueous solution having a monomer concentration of 20 to 60% by weight is polymerized in an oil-in-water type or water-in-oil type emulsified state using a hydrophobic solvent and an emulsifier.

The desired polymer can be obtained by subsequently partially hydrolyzing the (co) polymer obtained as described above. The hydrolysis may be performed under either acidic or basic conditions, but is preferably performed under basic conditions from the viewpoint of corrosion of the reactor. In the case of acid hydrolysis, the amino group of the vinylamine unit formed by hydrolysis is in the form of a salt, while in the case of basic hydrolysis, the amino group is in a free form. However, some or all of the free amine may be converted to a salt form by adding an acid after the hydrolysis.

As the acid compound used in the acidic hydrolysis, a strongly acidic compound is preferred, and hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, nitric acid, phosphoric acid, and sulfuric acid are preferred. Amic acid, methanesulfonic acid and the like can be mentioned, but monovalent acids are preferred in view of the solubility of the hydrolyzate in water. The basic compounds used in the basic hydrolysis include sodium hydroxide and potassium hydroxide. Lithium hydroxide, quaternary ammonium hydroxide oxide, ammonia, and low molecular weight primary Amin, secondary amiin, etc. are exemplified.

The acid or base is generally used appropriately in an amount in the range of 0.1 to 5 moles per mole of the amide group in the (co) polymer, depending on the desired modification ratio. The reaction temperature is preferably in the range of 50 to 110 ° C, and the reaction time is preferably in the range of 1 to 8 hours. Further, the hydrolysis is not limited to the aqueous solution state, and can be carried out in various situations, and may be a mixed solvent system of water and alcohol, a heterogeneous solvent system of water and hexane, toluene, or the like. Further, a method may be used in which the solid polymer in contact with water is brought into contact with a gaseous acid.

At the time of the above hydrolysis, hydrolysis may be optionally performed by adding a gelling inhibitor such as hydroquinamine hydrochloride or hydroxylamine sulfate for the purpose of preventing gelation caused by impurities. In general, it is particularly preferable to carry out the hydrolysis after the treatment with this gelling inhibitor for the hydrolysis.

The method for treating the dyed product with the dye fixing agent of the present invention is not particularly limited, and a conventionally known method can be appropriately used.

Examples of the cellulose fiber to which the dye fixing agent of the present invention is applied include cotton and rayon, and the present invention is also applicable to a composite fiber of a cellulose fiber and other fibers such as polyester and silk. The reactive dye for dyeing cellulose fibers is not particularly limited as long as it is a general dye, and water-soluble anionic dyes include vinylsulfone, dichlorotriazine, monochlorotriazine, and dichlorotriazine. Organic dyes having a reactive group such as a quinoxaline group can be used. Examples of the dyeing method include ordinary immersion dyeing, continuous dyeing, and print dyeing. As a method of treating a dyed product with the dye fixing agent of the present invention, for example, after immersing the dyed product to be treated in an aqueous solution of 1 to 5 g / ^ of the above polymer, squeezing with a mangle or the like, and heat drying. The method and the dyeing to be treated in an aqueous solution of 0.1 to 5 gZ of the above polymer may be immersed for 5 to 30 minutes at room temperature to 80, washed with water and dried.

Hereinafter, the present invention will be further described with reference to Examples. However, the present invention is not limited to these examples.

Example 1

62 g of water was added to 20 g of N-vinylformamide, the aqueous solution of the monomer was heated to 60, and 0.5% by weight of azobis (2-amidinopropane) hydrochloride was added to the monomer. And polymerized for 8 hours. After completion of the polymerization, 29.4 g of 35% hydrochloric acid (1 equivalent to N-vinylformamide) was added, and the mixture was hydrolyzed at 80 ° C for 5 hours, and the polymerization solution was precipitated in methanol. After filtration, the filtrate was dried under reduced pressure to obtain white polyvinylamine hydrochloride. The conversion was 98%.

Example 2

N-vinylformamide (10 g) and dimethyldiarylammonium chloride (10 g) are added with water (71 g), and the aqueous solution of the monomer is heated to 60 ° C, and then azobis (2-amidinopropane) hydrochloride is added. The salt was added in an amount of 0.5% by weight based on the amount of the monomer, followed by polymerization for 8 hours. After the completion of the polymerization, 14.7 g of 35% hydrochloric acid (1 equivalent to N-bulformamide) was added, and the mixture was hydrolyzed at 80 to 5 hours, and the polymerization solution was precipitated in methanol. After filtration, the filtrate was dried under reduced pressure to obtain a white copolymer of polyvinylamine hydrochloride and dimethyldiaryldimethyl chloride. The polymerization rate was 95%.

Example 3

N — for 10 g of vinylformamide and 10 g of acrylonitrile After adding 71 g of water and heating the aqueous monomer solution to 60 ° C., 0.5% by weight of azobis (2-amidinopropane) hydrochloride was added to the monomer, followed by polymerization for 8 hours. After completion of the polymerization, 14.7 g of 35% hydrochloric acid (1 equivalent to N-vinylformamide) was added, and the mixture was hydrolyzed at 80 ° C for 5 hours, and the polymerization solution was precipitated in methanol. After filtration, the filtrate was dried under reduced pressure to obtain a white copolymer of polyvinylamine hydrochloride and acrylonitrile. The conversion was 96%.

Example 4

To 10 g of N-vinylformamide, 5 g of dimethyldiarylammonium chloride and 5 g of acrylonitrile, 1 g of water J is added, and the aqueous solution of the monomer is heated to 60 ° C, and then the azobis (2— Amidinopropane) hydrochloride was added in an amount of 0.5% by weight with respect to the monomer, and polymerized for 8 hours. After the polymerization was completed, 14.7 g of 35% hydrochloric acid (1 equivalent to N-vinylformamide) was added, and the mixture was hydrolyzed at 80 ° C for 5 hours, and the polymerization solution was precipitated in methanol. After filtration, the filtrate was dried under reduced pressure to obtain a white copolymer of polyvinylamine hydrochloride, dimethyldiallylammonium chloride and acrylonitrile. The conversion was 95%

Example 5

To a 1 ^ reactor equipped with a stirrer, a nitrogen inlet tube and a cooling tube, 19 1 g of demineralized water was charged, and nitrogen was passed through the system at room temperature to degas. Subsequently, the temperature was raised to 70 ° C., and 6 g of a 10% aqueous solution of 2,2′-azobis-2-amidinopropane dihydrochloride was added. 69.9 g (purity 85.7%) of N-vinylformamide and 30.1 g of deionized water were added thereto. The pH was adjusted to 6.5 with a 1N aqueous sodium hydroxide solution. The resulting monomer solution was added over 2 hours. One hour after the start of the addition, 3 g of a 10% aqueous solution of 2,2'-azobis-1-2-amidinopropane 'dihydrochloride Was added, and the mixture was further reacted for 3 hours to obtain a 20% by weight solution of an N-vinylformamide polymer.

200 g of the obtained aqueous solution of N-vinylformamide polymer was placed in a reactor equipped with a stirrer and a temperature controller, and 0.52 g of hydroxylamine sulphate was added thereto. After stirring for 1 hour at room temperature, 53.8 g of a 35% by weight aqueous sodium hydroxide solution was added, and the mixture was heated and subjected to basic hydrolysis at 80 ° C for 5 hours. Thereafter, the temperature was returned to room temperature, and the pH was adjusted to 7.5 by adding 24.5 g of a 25% hydrochloric acid aqueous solution.

Analysis of the obtained polymer revealed that 35 mol% of the structural unit N-vinylformamide units and 65 mol% of vinylamine units were obtained.

Evaluation of sweat fastness

4 g ^ aqueous solutions of each of the polymers obtained in Examples 1 to 5 were prepared. Then, the cotton cloth continuously dyed at a concentration of 5% (by weight of fiber) is immersed in this solution using the following reactive dye, mangled, and heat-treated at 150 ° C for 90 seconds. Was performed. The drawing ratio at that time was 70%. The dyes used were Rikai On Red P-4BN and Rikai On Blue P-5R (Nippon Kayaku Co., Ltd.).

Similarly, a 4 gZ aqueous solution of a polymer of monoallylamine hydrochloride was prepared and treated in the same manner as above, and this was used as a comparative example.

The continuous dyed cloth used for the test was dyed under the following conditions.

Dyeing bath formula (g ^)

Dye X

Alginate reader 0.5

Urea 1 0 0

Soda ash 1 5 Sodium metanitrobenzenesulfonate 5 Treatment method

Processing is performed in the following order from ① to ④.

① Pad

② Dry (105 ° C x 3 minutes)

③ Baking (160 ° C x 2 minutes)

④ Soaking (90 ° C x 5 minutes)

Next, the sweat fastness of the treated dyed cloth was evaluated by JISL-0848 (Alli Sweat Method). The results are summarized in Table 1.

Table 1 Sweat fastness

A: Cotton-contaminated cloth B: Silk-contaminated cloth

The evaluation values in Table 1 are obtained by evaluating the contamination of the white cloth (cotton, silk) before and after the test using the gray scale for contamination. This evaluation value is classified into 5, 4, 1, 5, 4, 3—4, 3, 2—3, 2, 1—2 and 1.The higher the value, the smaller the contamination and the better the robustness. Means.

Evaluation of chlorine fastness Four aqueous solutions of each of the polymers obtained in Examples 1 to 5 were prepared. Then, a cotton cloth continuously dyed at a concentration of 0.5% (based on the weight of the textile) is immersed in the solution using the reactive dye described below, mangled, and subjected to 150 ° C for 90 seconds. Heat treatment was performed. The drawing ratio at that time was 70%. The dyes used were Cibacron Blue 3R (manufactured by Ciba Geigy Corporation) and Rikiyashion Gray P-NR (manufactured by Nippon Kayaku Co., Ltd.).

Similarly, a 4 gZ ^ aqueous solution of a polymer of monoallylamine hydrochloride was prepared and treated in the same manner as above, and this was used as a comparative example. The continuous dyed cloth used for the test was dyed in the same manner as the dyed cloth used for the evaluation of sweat fastness.

Next, the chlorine fastness of the treated dyed fabric was evaluated by JISL-08884 (weak test and strong test). The results are summarized in Table 2, Table 2 Chlorine fastness

A: Weak test B: Strong test

The evaluation values in Table 2 were obtained by evaluating the discoloration and fading of the treated dyed cloth before and after the test using a gray scale for discoloration. This evaluation value is It is classified into 5, 4-5, 4, 3-4, 3, 2-3, 2, 1-2 and 1. The larger the value, the smaller the discoloration and fading, and the better the fastness.

Evaluation of heat treatment yellowing

A mixed aqueous solution of 4 g Z ^ of each of the polymers obtained in Examples 1 to 5 above and 3 g of the fluorescent dye Hatsukoru BRK (manufactured by Showa Chemical Industry Co., Ltd.) was prepared. Next, a cotton blown cloth was immersed in this solution, mangled, and heat-treated at 150 ° C for 90 seconds. The drawing ratio at that time was 70%.

Next, the whiteness of the treated cloth was measured using a colorimeter Macbeth Color Eye MS-220 (manufactured by Macbeth) to obtain a Hunter White Index (WI value). The higher the value of the WI value, the brighter the whiteness. Table 3 summarizes the results.

Table 3 Heat treatment yellowing

Raw fabric W I value: 8 8 Industrial applicability

According to the present invention, for a dyed product dyed with a reactive dye, chlorine fastness is improved, yellowing due to heat treatment is reduced, and wet fastness is improved. Can provide dye fixative to improve the degree

Claims

The scope of the claims

1. A dye fixing agent used for a cellulosic textile dyed with a reactive dye, which comprises a homopolymer containing a structural unit of vinylamine represented by the following general formula (I) and / or a salt thereof. Dye fixing agent.

— CH ₂ -CH-(I)

NH ₂

2. The dye according to claim 1, wherein the structural unit of vinylamine forms a salt with hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, sulfamic acid or methanesulfonic acid. Fixing agent.

3. A dye fixing agent used for a cellulosic textile dyed with a reactive dye, which is represented by the structural unit of vinylamine represented by the following general formula (I) and the following general formula (II): A copolymer and / or a salt thereof, wherein the structural unit of vinylamine is 5 to 90% by weight and the structural unit of diarylamine is 5 to 90% by weight. Dye fixing agent.

— C H C H-(I)

NH ₂

-CH ₂ -CH- CH- CH _2- (II)

I I-

C H 2 then 1 2

I

R

(Wherein, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

4. The dye according to claim 3, wherein the structural unit of vinylamine forms a salt with hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, sulfamic acid or methanesulfonic acid. Fixing agent.

5. The structural unit of diarylamine is hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, Form a salt with formic acid, acetic acid, propionic acid, sulfamic acid or methanesulfonic acid, or form an alkyl halide (alkyl having 1 to 4 carbon atoms), benzyl halide or dialkyl The dye fixing agent according to claim 3 or 4, wherein the dye fixing agent forms a quaternary ammonium salt with the alkylene having 1 to 2) sulfuric acid.

6. A dye-fixing agent used for a cellulosic fiber dyed with a reactive dye, comprising a vinylamine structural unit represented by the following general formula (I) and a vinyl copolymerizable with the vinylamine. A copolymer comprising the structural unit of the vinyl compound, wherein the structural unit of the vinylamine is 5 to 90% by weight, and the structural unit of the vinyl compound is 5 to 90% by weight, and / or a salt thereof; Alternatively, the structural unit of vinylamine represented by the following general formula (I), the structural unit of diarylamine represented by the following general formula (II), and the vinylamine and vinyl copolymerizable with the diarylamine. The structural unit of the vinylamine is 5 to 90% by weight, the structural unit of the diarylamine is 5 to 90% by weight, and the structural unit of the vinyl compound is 5 to 90% by weight There copolymers and Roh or dye fixing agent comprising a salt.

-CH ₂ CH-(I)

NH ₂

-CH ₂ -CH-CH-CH _2- (II)

C H 2 then H 2

I

R

7. The dye according to claim 6, wherein the structural unit of vinylamine forms a salt with hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, sulfamic acid or methanesulfonic acid. Fixing agent.

8. Whether the diarylamine structural unit forms a salt with hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, sulfamic acid, or methanesulfonic acid A quaternary ammonium salt is formed with an alkyl halide (alkyl having 1 to 4 carbon atoms), a benzyl halide or a dialkyl (alkyl having 1 to 2 carbon atoms) sulfuric acid. 6. The dye fixative according to 6 or 7.

9. When the vinyl compound is N-vinylformamide, N-vinylacetamide, N-vinylpropionamide, etc., N-vinylamide, styrene, N-methylolacrylamide, N-vinylamide — Methylarylamin, N—Ethylarylamine, N—Propylarylamine, N, N—Dimethylarylamine, N, N—Jetylarylamine, (Meth) acrylonitrile , (Meth) acrylamide, N—substituted (meth) acrylyl amide, (meth) acrylyl esters, vinylesters, vinylethers, non-ionic monomers such as vinyl alcohol and aryl ether Body, (meth) acrylic acid,, ^ -unsaturated dicarboxylic acid, sulfoalkyl (meth) acrylamide, sulfoalkyl (meta) acrylate, Claims selected from anionic monomers such as (meth) arylsulfonic acid, dialkylaminoalkyl (meth) acrylates, dialkyaminoalkyl (meth) acrylamides and arylamines Item 10. The dye fixative according to any one of Items 6 to 8.