JP2652475B2 - Dye-proofing method for cellulosic fiber products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for dyeing cellulosic fiber products.

[0002]

2. Description of the Related Art When dyeing a cellulosic textile using an addition-type reactive dye having a vinylsulfone group, at least one type of anti-staining agent selected from sulfites, acid sulfites and hydroxyalkyl sulfonates. When performing the anti-dyeing treatment with a colored anti-dyeing agent containing and a reactive dye having a chloro group, the amount of the anti-dyeing agent is adjusted to a necessary minimum amount capable of exhibiting an intended anti-dyeing effect. This is very difficult and generally requires the overuse of repellents. However, when an excessive amount of the anti-dyeing agent is used, since all of the anti-dyeing agents are water-soluble, they bleed and the printing pattern edge becomes blurred,
There is a drawback that a so-called haloing phenomenon occurs, which makes it difficult to obtain a product that can be commercialized.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for effectively dyeing cellulosic fiber products without causing a haloing phenomenon in the above-mentioned method.

[0004]

According to the present invention, there is provided a method for dyeing a cellulosic textile product with a dye composition containing an addition type reactive dye having a vinyl sulfone group, a sulfite, an acid sulfite and a hydroxyalkyl sulfone. A colored anti-staining paste containing at least one anti-staining agent selected from acid salts and a substituted-type reactive dye having a chloro group, which is subjected to an anti-dyeing treatment, and is an addition-type reactive dye having a vinyl sulfone group. By adding at least one type of anti-haling agent selected from the compounds represented by the following formulas (1) to (4) to the dyeing composition containing, a clear anti-dying dyeing without a haloing phenomenon on a cellulosic fiber product is enabled.

[0005]

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[0006]

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[0007]

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(Where R is a methyl group or hydrogen, S is an integer of 3 to 20, and P is an integer of 0 to 10)

The antihaloing agent of the formula (1) is a water-soluble or water-miscible compound, is capable of being uniformly mixed with the dyeing composition, and has an active vinyl bond at its terminal.
It binds and removes sulfurous acid and sulfonic acid (or sulfurous acid gas generated from the sulfuric acid) contained in an excessive amount of the anti-dyeing agent, and exhibits an effective antihaloing ability.
When S is 2 or less or P is 11 or more, it becomes insoluble in water and does not disperse and solubilize in water even when used together with a dissolution aid such as urea and methyl alcohol, and is uniform in a printing paste or pad dyeing bath. Therefore, a sufficient anti-halo effect cannot be expected. Further, when the chain length is as long as S + P is 31 or more, the activity of the terminal vinyl group is weakened, the bonding strength between sulfurous acid, sulfonic acid and the like and the antihaloing agent is weakened, and the desired antihaloing effect cannot be obtained.

[0010] The method of the present invention comprises the step of reacting a cellulosic fiber product with at least one kind of an anti-staining agent selected from sulfites, acid sulfites and hydroxyalkyl sulfonates and a substituted reactive dye having a chloro group. A method of dyeing with a dye composition (dying solution or printing paste) containing an addition type reactive dye having a vinyl sulfone group after printing of the contained colored anti-dyeing paste, and dyeing containing an addition type reactive dye having a vinyl sulfone group After dyeing with the composition (dyeing liquid or printing paste), any of the methods of printing with the above-mentioned colored anti-dyeing agent may be used, and in the method of the present invention, known compounds can be used as the anti-dyeing agent. . The following are typical examples:
The compound represented by these is mentioned.

[0011]

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(Wherein R ₁ is a saturated or unsaturated hydrocarbon chain having 1 to 5 carbon atoms, R ₂ is a hydrogen atom, a saturated or unsaturated hydrocarbon residue having 1 to 5 carbon atoms or a phenyl group, and Z Represents a monovalent metal element or an ammonium group.)

The formulation and the method of use of the colored anti-staining paste containing the above-mentioned anti-staining agent may be the same as those of the ordinary anti-staining paste, and the compounding amount of the anti-staining agent is also the usual amount, for example, 0. 5
The content may be 10 to 10% by weight, preferably 1 to 5% by weight.
In addition, this anti-staining paste is a normal paste, typically sodium alginate, highly etherified carboxymethyl cellulose,
Processed starch, natural gum, carboxyvinyl compound, etc. and O
/ W-type emulsion paste, W / O-type emulsion paste and the like, and if necessary, an alkali or alkali generator such as sodium bicarbonate and sodium silicate may be added. Further, the above-mentioned anti-dyeing paste contains a substitution type reactive dye having a chloro group, for example, Procion (manufactured by ICI), Cibacron (manufactured by Ciba Geigy), Dorimalen (manufactured by Sandos), Levafix (Bayer) Can be used.

Next, the dyeing composition containing the above-mentioned anti-haling agent is prepared by adding a reactive dye having a vinyl sulfone group, for example, Remazol (manufactured by Hoechst), Sumifix (manufactured by Sumitomo Chemical Co., Ltd.), Sermazole ( Mitsui Toatsu Dye Co., Ltd.) and Diamira (Mitsubishi Kasei Hoechst Co., Ltd.) can be added and used. In addition, a paste for printing and various auxiliaries may be added to the dyeing composition, and these may be the same as the above-mentioned colored paste.

[0015] The amount of the antihalo agent used in the dyeing composition is usually about 0.5 to 20% by weight, preferably about 1 to 5% by weight.

The method for applying the anti-paste paste and the dyeing composition to cellulosic fiber products may be in accordance with known methods.
There is no particular limitation. For example, methods such as roller printing, screen printing, and hand printing can be used.
Any method such as post-dyeing or bat method can be applied. Depending on the purpose, the color development method subsequent to printing may also be any of various known methods such as a normal pressure steaming method, an alkali shock method, a thermosol method,
Any of the HT steam method and the like can be applied, and there is no possibility of discoloration of the ground color by any method.

The cellulosic fiber products treated in the present invention refer to various cellulosic fiber products which can be dyed with a reactive dye, and include cellulose fibers such as cotton, hemp, rayon, polynosic, cupra and the like. yarn,
Knitted fabrics, woven fabrics, non-woven fabrics, and blends of the above-mentioned cellulose fibers and other fibers such as nylon, polyester, acrylic, acetate, wool, and the like, as well as cross-woven and cross-knitted fabrics are all included.

[0018]

EXAMPLES Next, examples will be given to explain the present invention in more detail. In each Example, “parts and%” means “parts by weight” and “% by weight” unless otherwise specified. Example 1 A colored anti-dyeing paste having the following composition was printed on a No. 60 broad cotton cloth. Cibacron Red B ^{* 1} 30 parts Urea 100 parts MS liquid ^{* 2} 20 parts Sodium sulfite 30 parts Hot water 300 parts Sodium alginate (5%) 500 parts Sodium bicarbonate 20 parts 1000 parts * 1) Reactive dye manufactured by Ciba Geigy. * 2) An anti-reducing agent manufactured by Meisei Chemical Industry Co., Ltd. After the above printing, the colored printing paste having the following composition was partially overlapped on the same cotton cloth without drying, and printing was sequentially performed. Sumifix Brilliant Blue R ^{* 3} 20 parts Urea 50 parts MS Liquid ^{* 1} 20 parts Hot water 370 parts Sodium alginate (5%) 500 parts Sodium bicarbonate 20 parts Antihaloing agent ^{* 4} 20 parts 1000 parts * 3) Sumitomo Chemical Co., Ltd. Reactive dyes. * 4) A compound of the general formula, wherein R is hydrogen, S is 16, and P is 0.
Polyoxyethylene diacrylate. After overlay printing of the colored printing paste, the printed fabric obtained by steaming at 100 ° C. for 8 minutes was washed with water, washed with hot water, soaped, washed with water, dehydrated, and dried. For comparison, a printed fabric was obtained by combining and printing the anti-staining paste and the colored printing paste in exactly the same manner as described above except that the anti-halo agent was not added to the above-described anti-staining paste. According to the method of the present invention, the printing cloth to which polyoxyethylene diacrylate (S = 16) was added as an antihalo agent did not show any haloing phenomena. The printing cloth to which ethylene diacrylate (S = 16) was not used clearly had a haloing phenomenon, and a product having commercial value could not be obtained.

Example 2 A colored anti-dyeing paste having the following composition was printed on a No. 60 broad cotton cloth. Procion Blue H-3R ^{* 5} 30 parts Urea 100 parts MS Liquid ^{* 1} 20 parts Sodium hydroxymethanesulfonate 40 parts Hot water 290 parts Sodium alginate (5%) 500 parts Sodium bicarbonate 20 parts 1000 parts * 5) I. C. I. After the above-mentioned printing, the colored printing paste having the following composition was partially overlapped with the same cotton cloth, and the printing was performed sequentially. Sumifix Red B ^{* 6} 20 parts Urea 50 parts MS Liquid ^{* 1} 20 parts Hot water 380 parts Sodium alginate (5%) 500 parts Sodium bicarbonate 20 parts Antihaloing agent ^{* 7} 10 parts 1000 parts * 6) Sumitomo Chemical Co., Ltd. Reactive dye. * 7) A polyoxyethylene diglycidyl ether-acrylic acid adduct of the general formula, wherein R is hydrogen, S is 9, and P is 0. After printing, the printed fabric obtained by steaming at 103 ° C. for 3 minutes was washed with water, washed with hot water, soaped, washed with water, dehydrated, and dried. As a result, a printed matter having a sharp edge and no haloing phenomenon was obtained. On the other hand, a printed fabric obtained by performing the same method as the above method except that no haloing agent was added to the anti-paste paste had a haloing phenomenon, and was a product with a white and blurred edge. Was.

Example 3 A No. 60 broad cotton cloth was continuously immersed in a colored pad solution having the following composition, then squeezed (a squeezing ratio of 80%) and dried. Remazol black B ^{* 8} 100 parts Urea 100 parts MS liquid ^{* 1} 20 parts Hot water 650 parts Sodium alginate (5%) 100 parts Sodium bicarbonate 20 parts Antihaloing agent ^{* 9} 10 parts 1000 parts * 8) Reactive dye manufactured by Hoechst. * 9) A compound of the general formula, wherein R is hydrogen, S is 16, and P is 4.
Polyoxyethylene polyoxypropylene trimethylolpropane triacrylate. Thereafter, the same cotton cloth dyed black was printed with a colored paste having the following composition. Cibacron Turkis Blue GF-P ^{* 10} 30 parts Urea 100 parts MS liquid ^{* 1} 20 parts Sodium sulfite 30 parts Hot water 300 parts Sodium alginate (5%) 500 parts Sodium bicarbonate 20 parts 1000 parts * 10) Reactive dye manufactured by Ciba Geigy . After printing the colored anti-dyeing paste, it is dried, and the dyed cloth obtained by steaming at 105 ° C. for 3 minutes is washed with water, washed with hot water, soaped, washed with water,
Dehydrated and dried. As a result, a printed matter having a sharp edge and no haloing phenomenon was obtained. On the other hand, the printed fabric obtained by performing the above method without using the halo agent had a halo phenomenon, and was a white and blurred product.

[0021]

According to the anti-dyeing method of the present invention, it is possible to obtain a printing cloth having a sharp edge without a haloing phenomenon.

Claims (1)

(57) [Claims] When dyeing a cellulosic fiber product with a dyeing composition containing an addition-type reactive dye having a vinyl sulfone group, at least one kind of protection selected from sulfites, acid sulfites and hydroxyalkyl sulfonates. A dye-resisting paste containing a dye and a substitution-type reactive dye having a chloro group, which is subjected to anti-dyeing treatment, wherein the dyeing composition containing the addition-type reactive dye having a vinyl sulfone group has the following formula:
At least one antihaloing agent selected from the compounds represented by Embedded image Embedded image (Wherein R is a methyl group or hydrogen, S is an integer of 3 to 20, and P is an integer of 0 to 10).