JPH0146638B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an anti-discharge printing method for polyester/cellulose fiber mixed structures, and more particularly to an anti-discharge printing method that uses a specific disperse dye and carries out anti-discharge printing and coloring in the presence of an alkali. Conventionally, methods for uniformly dyeing polyester/cellulose fiber mixed structures include disperse dyes/substitution reaction type reactive dyes (e.g., monochlorotriazine type), disperse dyes/addition reaction type reactive dyes (e.g., vinyl sulfone type), and disperse dyes. dye/direct dye,
Disperse dyes/butt dyes, disperse dyes/sulfur dyes, disperse dyes/naphthol dyes, diblen dyes (EI
Dupont), pigments, and alkali-soluble disperse dyes (ICI, Dispasol PC)/special substitution reaction type reactive dyes (ICI, Procion T), etc. are known. However, in the combination of disperse dye/substitution reactive dye, thermosol,
Polyester/cellulose fiber mixed structures (hereinafter abbreviated as P/C structures) can be uniformly dyed by high temperature steaming (HTS), high pressure steaming (HPS), etc., but discharge printing is difficult and coloring and discharge printing is difficult. is completely unsuitable. Furthermore, fabrics dyed with disperse dyes/sulfur dyes, disperse dyes/naphthol dyes, diblen dyes, etc. are also difficult to discharge print, and it is completely impossible to print distinct colors. It is also possible to use pigment printing technology for differential colors, but it cannot be used because it cannot be discharge printed for ground colors and the texture is hardened. On the other hand, an anti-discharge printing method is also being considered that uses an alkali-soluble disperse dye and an addition-reactive reactive dye as the ground color, and an alkali-resistant disperse dye and/or a substitution-reactive reactive dye as the accent color. Since the washing fastness and chlorine fastness are poor, it is unsatisfactory for applications that require strong washing fastness, such as sports clothing. In view of the above-mentioned circumstances, the present inventor conducted extensive research and arrived at the method of the present invention. That is, the present invention uses polyester.
After applying a dye liquor or printing paste containing (a) an alkali-soluble disperse dye and (b) an addition reaction type reactive dye as essential components to the cellulose fiber mixed structure, (c) a vat dye, and (d) Imprinting or partial application of a dye liquor or printing paste containing an alkaline agent and (e) reducing agent as essential components, or dye liquor or printing paste containing the above components (c), (d) and (e) as essential components. After stamping or partially applying glue (a) above
This is an anti-discharge printing method for a polyester/cellulose fiber mixed structure, which is characterized by applying a dye liquor or printing paste containing component (b) as an essential component, followed by drying and fixing treatment. According to the method of the present invention, the P/C structure has excellent clarity and mold edge sharpness, and also has good washing fastness.
It is possible to provide a discharge-resistant product with excellent chlorine fastness. The method of the present invention will be explained in more detail below. The polyesters used in the present invention include polyethylene terephthalate, polybutylene terephthalate, polyoxyethoxybenzoate, polyethylene naphthalate, cyclohexane dimethylene terephthalate, and dicarboxylic acids such as isophthalic acid, adipic acid, and sulfoisophthalic acid as an additional component to these polyesters. Examples include polyesters copolymerized with acid components, diol components such as propylene glycol, butylene glycol, cyclohexanedimethanol, and diethylene glycol, and modified polyesters blended with polyalkylene glycols. Further, examples of cellulose include cotton, linen, viscose rayon, polygonal crayon, copper ammonium rayon, and the like. These fiber mixed structures include yarns, knitted fabrics,
Examples include non-woven fabrics, rugs, tapes, etc., and the mixing form may be arbitrary such as blended yarns, mixed fibers, mixed weaves, mixed knits, and composite yarns such as cover yarns. The alkali-soluble disperse dye used in the present invention is a type of disperse dye that is solubilized or decomposed and solubilized by an alkali, for example, a disperse dye having at least one carboxyl group, carboxylic acid ester group, etc. in the molecule. Dyes are preferred. Examples of the disperse dye include the dyes disclosed in Japanese Patent Application Laid-Open No. 186980/1983. However, nitrothiazole azo dyes which are decomposed and solubilized by alkali can also be used. Further, as the addition reaction type reactive dye, vinyl sulfone type, α-bromoacrylamide, etc. are preferable. The method for applying it to the P/C structure may be a normal method. In the present invention, the alkaline agents used for resist discharge printing include alkali hydroxides such as sodium hydroxide and potassium hydroxide, alkali carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate, and sodium silicate. , alkali silicates such as potassium silicate, inorganic alkalis such as alkali phosphates such as trisodium phosphate and tripotassium phosphate, organic carboxylic acids such as trichloroacetic acid, acetic acid, formic acid, cyanoacetic acid, acetone dicarboxylic acid, acetoacetic acid, and diethoxalic acid. Examples include organic alkalis such as alkali metal salts of acids and quaternary ammonium hydroxides. Particularly preferred alkalis include alkali carbonate, alkali bicarbonate, alkali silicate,
A weak or latent alkali such as an alkali metal salt of an organic carboxylic acid. The amount of the alkali agent used varies mainly depending on the type of alkali, the type of reactive group in the reactive dye, etc., but it is usually 0.5 to 12% by weight, preferably 1 to 12% by weight, based on the discharge-proof printing paste.
It is 10% by weight. Of course, two or more alkaline agents may be used in combination. Furthermore, dyes with a high reduction potential are preferably used as batt dyes for use in contrast colors. When vat dyes are used for discharge-proof printing, a moisture absorbent (hydrotrope) is usually used to promote reduction and dyeing of accent colors. Examples include glycerin, ethylene glycol, diethylene glycol, polyethylene glycol, and thiodiethylene glycol, but when using an alkali-soluble disperse dye for the ground color as in this method, the alkaline discharge printing aid can also serve as a moisture absorbent. . For example, anionic compounds having an alkylene oxide unit as a linking member and/or esters thereof are widely mentioned. R{X [(AO) _n R'Y] _o } _p where R: substituted or unsubstituted alkyl group, aryl group, aralkyl group, alkylene group, arylene group, etc. X: -O-, -COO-, - N=, −NR″−, −
S−, −CONR″−, −CON=, −
SONR''-, -SON= etc. R': Divalent linking group such as alkylene group or arylene group R'': Hydrogen atom or alkyl group A: Alkylene group m: Positive integer, preferably an integer from 2 to 20 n: 1 or 2 p: Integer from 1 to 6 Y: _-SO3M , -PO(OM) ₂ , -COOM,

[Formula] -PO(OM)(OR), -PO(OR) ₂ , etc. R: Alkyl group, aryl group, (-AO) - _n
R etc. R′′′′: Alkyl group, aryl group, acyl group, etc. M: Hydrogen atom, alkali metal, ammonium group, or organic amine group More specifically, fatty acid, alcohol, alkylamine, alkylmercaptan, fatty acid amide,
Sulfuric esters of adducts of phenols, alkylsulfonamides, alkylene diamines, etc. and alkylene oxides, their alkali salts, ammonium salts, fatty acids, alcohols, alkylamines, alkylmercaptans, fatty acid amides, phenols, alkylsulfonamides, alkylene diamines, etc. Examples include sulfonated alkylene oxide adducts. Part or all of the ethylene oxide units in the above compound may be replaced with propylene oxide units, and some of them may also be replaced with butylene oxide units or the like. When two or more types of alkylene oxide units are included, the bonding form may be either block or random. The amount of the above-mentioned moisture absorbent/discharge-proof dyeing aid used varies depending on the mixing ratio of the P/C structure and the dye concentration used, but is preferably 0.5 to 15% by weight, and particularly preferably 2 to 10% by weight. . Also, as a reducing agent, Superite C
( _NaHSO2・_CH2O・_2H2O ), _ZnSO2・_CH2O・
_H2O , Redor ZW “Zn( _HSO2・_CH2O ) ₂ ”,
ZnSO ₂・CH ₂ O・H ₂ O, Na ₂ S ₂ O ₅ , zinc salt of hydroxymethasulfinic acid, organic tin compounds such as stannous chloride, thiourea dioxide, and stannous acetate are used. be done. In the present invention, after applying the above-mentioned alkali-soluble disperse dye and addition reaction-type reactive dye to the entire surface or part of the P/C structure by any method, printing paste containing the above-mentioned vat dye, alkaline agent, and reducing agent is applied. Overprint by printing, coating, etc. as a differential color prescription. For fixation of the ground color, a reactive dye fixation improver such as sodium trichloroacetate may be used in combination. The above has explained discharge printing, but by reversing the order of application of the ground color and the difference color, that is, by overprinting the ground color on the entire or partial surface of the P/C structure printed with the difference color prescription, coloring is achieved. It can also be resist dyed. After applying the ground color and differential color, drying and fixing treatments are usually performed. As a fixation treatment method, for example, 2
After HTS (high temperature steaming) treatment for ~10 minutes, thermosol at 190-220℃ for 6-90 seconds, or at 160-180℃ for 5-15 minutes.
After HTS treatment or HPS (high pressure steaming) treatment at 120-130℃ for 20-30 minutes, 85
Examples include RC (reduction cleaning) shock at ~90°C for 10 to 60 seconds or cold fixing at room temperature for 15 minutes to 24 hours. For deep color dyeing, 100-150℃ prior to HTS treatment.
Pre-steaming for about 2 to 10 minutes can also be performed. However, especially if the background color is light, pre-steaming is not necessary. After the fixation process, the dye is washed with water, oxidized, and washed with water in the same way as in the vat dyeing process. The present invention will be explained in more detail with reference to Examples below. Note that parts and percentages in the examples are based on weight. Example 1 A polyester/cotton blend (65/35%) broadcloth was dipped in a dye solution with the following ground color formula, and after squeezing to a squeezing rate of 60%, it was dried intermediately, and then a printing paste with the following difference color formula was flat-screened. After overprinting the floral pattern, after drying, HTS treatment at 105℃ for 7 minutes,
HTS treatment at 170°C for 10 minutes followed by RC shock treatment at 90°C for 30 seconds to fix the dye, followed by washing with water, oxidation, and soaping.

【table】

[Table] Differential color formula 15% Sorbitose C-5 (Skolten, modified starch) 50 parts Potassium carbonate 8 parts Rongarit C (BASF, reducing agent) 8 parts Glycerin 5 parts Mikethrene Brilliant Pink R (Mitsui Toatsu) ,
Batt dye) 4 parts Water 25 parts Total amount 100 parts As a result, a colored discharge-printed product having a pink floral pattern on a vivid red background was obtained. In addition, there was almost no decrease in the strength of the cotton portion. The washing fastness and chlorine fastness were also good. Example 2 A polyester/polynojitsu crayon staple blend (65/35%) fabric was dipped in a dye solution with the following ground color formula, squeezed at a squeezing rate of 65%, and dried midway, followed by the difference color formula of Example 1. 165 after printing with printing paste and intermediate drying
After HTS treatment for 10 minutes at ℃, the dye was fixed for 4 hours at room temperature using the usual cold fix method, washed with water, and then subjected to the usual oxidation treatment in the vat dyeing method and soaped. Different color formula Kayalon Polyester Blue BD-S Conch (Nippon Kayaku Co., Ltd., alkali-soluble disperse dye) 2 parts Sumifix Blue 2RB (Sumitomo Chemical Co., Ltd., vinyl sulfone-based reactive dye) 1 part 5% sodium alginate aqueous solution 10 parts Water 87 parts Total amount 100 parts As a result, a brightly colored discharge-printed product with a pink floral pattern on a uniform blue background was obtained. The washing fastness and chlorine fastness were also good. Example 3 A polyester/cotton blend (65/35%) jersey was colored and resist-dyed using a dye solution with the following background dyeing formula and a resist dyeing paste with a difference color formula, and then subjected to the same fixing treatment and soaping as in Example 1. Ivy. Ground color prescription dispasol black 2R-PC (liquid)
(ICI, alkaline hydrolyzable disperse dye) 10 parts Sumifix Black B (Sumitomo Chemical, vinyl sulfone reactive dye) 5 parts 1% sodium alginate aqueous solution 50 parts Water 35 parts Total amount 100 parts

[Table] As a result, a clear floral pattern with purple resist dyeing on a uniform black background was obtained. The washing fastness and chlorine fastness were also good. Example 4 A polyester/cotton blend (65/35) broadcloth was immersed in a dye solution with the following ground color formula, and after squeezing to a squeezing rate of 60%, it was dried intermediately, and then a printing paste with the following difference color formula was applied using a flat screen. A floral pattern was overprinted, dried, treated with HTS at 160℃ for 15 minutes to fix the dye, washed with water, oxidized, and soaped.

[Table] Differential color prescription 12% Maypro Gum NP (Mayhole, Guar Gum)
25 parts 15% Sorbitose C-5 25 parts Mikethrene Orange R (Mitsui Toatsusha, Vatu Dye)
5 parts Potassium carbonate 6 parts Rongarit C 6 parts Ethylene glycol 4 parts Water 29 parts Total amount 100 parts As a result, the dyed cloth obtained was a clear difference color discharge-printed product with an orange floral pattern on a uniform red background. Ta. The washing fastness and chlorine fastness were also good.

Claims (1)

[Claims] 1. After applying a dye liquor or printing paste containing (a) an alkali-soluble disperse dye and (b) an addition reaction type reactive dye as essential components to a polyester/cellulose fiber mixed structure, (c) a butt dye, ( d) Printing or partial application of a dye liquor or printing paste containing an alkaline agent and (e) a reducing agent as essential components, or a dye liquor containing the above components (c), (d) and (e) as essential components. Or a polyester/cellulose fiber mixture characterized in that after printing or partially applying a printing paste, a dye liquor or printing paste containing the above components (a) and (b) as essential components is applied, followed by drying and fixing treatment. Anti-discharge method for structures.