JPS6254916B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a discharge printing method suitable for polyester fiber products. Discharge printing has many advantages as a high-quality printing technology, such as the ground color is dyed on the back of the fabric, and the ground color is deep, it produces delicate patterns with no pattern deviation, and there is no boundary line between areas. , which has been applied to various fiber materials. Discharge printing technology has also been studied for polyester fiber materials, but the results are not yet satisfactory. Ground dyeing methods for discharge printing include high-temperature dyeing, carrier dyeing, and padding dyeing, but high-temperature dyeing is often used because it allows for easy level dyeing. In general, sulfine compounds are used as a discharge printing agent for polyester textile products in the case of white discharge printing.
In the case of colored discharge printing, stannous compounds are used. Examples of sulfin compounds include Zn (HSO ₂
CH ₂ O) ₂ , ZnSO ₂・CH ₂ O ・H ₂ O, etc., and stannous compounds include stannous chloride, stannous acetate, stannous phosphate, stannous oxalate, stannous fluoride, etc. Tin etc. are used. When discharging polyester fiber material that has been ground-dyed using a high-temperature dyeing method, sulfin compounds,
Although stannous compounds and stannous compounds are suitable as discharge printing agents, the discharge printing effect is often insufficient with these alone, and it is usually necessary to use a compound with a discharge promoting effect in order to enhance the discharge printing effect. As this compound, diphenyl, phenol derivatives, especially p-phenylphenol,
and its alkylene oxide adducts have been used. Although these compounds have an excellent effect of accelerating discharge printing, they often remain in the fibers and cannot be removed even by high-temperature dry heat treatment, resulting in the problem that they significantly reduce the light fastness of the ink color in colored discharge printing. The dot was hot. The present inventors promote the discharge printing effect of such a discharge printing agent by using it in combination with a discharge printing agent selected from the group consisting of sulfin compounds and stannous compounds,
Furthermore, as a result of repeated research into compounds that do not reduce the light fastness of the ink color dyes, the present invention was achieved by discovering that a compound represented by the following general formula is excellent in such effects. That is, the present invention provides at least one discharge printing agent selected from the group consisting of sulfinic compounds and stannous compounds, and the following general formula (1). However, R ₁ and R ₂ are H, an alkyl group, halogen R ₃ is a C ₁ to C ₄ alkyl group, or R ₄ is −CH ₂ −CH ₂ −, −CH=CH− −CH ₂ −
CH(OH)- m is 0 or 1 n is 1 to 10 A discharge printing process is carried out on polyester fiber products using a discharge printing paste containing a compound represented by the following formulas. The compound of general formula (1) is phenol, cresol,
Ethylene oxide is added to xylenol, ethylphenol, monochlorophenol, dichlorophenol, etc., and then (a) an alkylating agent (alkyl halide, dialkyl sulfate) is reacted in the presence of an alkali, (b) acetic acid, propionic acid Esterification with etc.
Alternatively, (c) it can be obtained by reacting with a dibasic acid such as succinic acid, maleic acid, or malic acid to form a diester. Specific examples of the structural formulas of the compounds used in the present invention are as follows. (a) m=0, R ₃ is an alkyl group (b) m=1, R ₃ is an alkyl group (c) m=1 The amount of the above compound to be used is preferably about 2 to 10% by weight in the discharge printing paste, and usually 3 to 6% by weight is particularly preferably used. Since this compound is insoluble or sparingly soluble in water, it is preferable to add and use appropriate auxiliary agents such as emulsifiers, solvents, and sizing agents when using it, and the combined use of these agents will not reduce the discharge printing effect. The method of the present invention can be applied to polyester fiber products, and of course can be applied to other fibers such as cotton,
Blends with wool, silk, nylon, acrylic, etc.
It can also be applied to mixed woven products. Furthermore, polyester fiber products include not only those dyeable with disperse dyes, but also those modified to be dyeable with cationic dyes and acid dyes. It is preferable to select a dye that is weak against reduction (removable dye) as the dye for ground dyeing such textile products, and a dye that is strong against reduction as the insert color dye for color discharge printing.
In the present invention, by using the compound represented by the general formula (1), the whiteness of the discharge-printed area is vivid, the color development of the ink color dye is excellent, and the light fastness is good. A discharge printing paste with the following composition was printed on a polyester palace, and high temperature steam was applied at 175℃ x 8 minutes.
Table 1 shows the results of measuring the light fastness of each compound. In the method of the present invention, no decrease in light fastness due to the addition of auxiliary agents is observed.

【table】

[Table] Next, examples of the present invention are shown.
"" indicates parts by weight and weight %, respectively. In addition, in the examples, the white-out effect and the removal effect were expressed as 〇...Good and ◎...Excellent. Example 1 Polyester dioset was dyed at 130% in the following dye bath.
Staining was carried out at ℃ for 60 minutes. Dye bath Miketon Discharge Yellow 3G ^*1 3.0%owf Miketon First Pink FR ^*1 2.5%owf Miketon Polyester Discharge Blue R ^*1 9.5%owf 15.0%owf Next, the following discharge printing paste is printed on the obtained ground-dyed fabric and dried. After that, a high-temperature steam treatment was performed at 175°C for 8 minutes, followed by washing by a conventional method.

[Table] As a result, a discharge printed cloth with extremely excellent whiteness was obtained. Example 2 A method similar to Example 1 was carried out using the following compound as an auxiliary agent for discharge printing paste.

【table】

[Table] Example 3 The same dyed fabric as in Example 1 was printed with a discharge printing paste according to the following process, and after drying, it was subjected to a high-temperature steam treatment at 175°C for 8 minutes. Maypro Gum NP (12%) 50 parts Stannous chloride 8 Urea 5 Water 32 Auxiliary agent ^* 5 100 *The following compounds were compared as auxiliary agents.

[Table] Example 4 The same dyed fabric as in Example 1 was printed with a discharge printing paste having the following formulation.

[Table] The blue color was vividly dyed, and its light fastness was almost the same as when no auxiliary agent was added. Example 5 The same method as in Example 4 was carried out using the following compound as an auxiliary agent for the discharge printing agent.

【table】

[Table] A discharge-printed fabric with clear color and excellent light fastness was obtained. Example 6 A polyester fiber product dyeable with cationic dyes was dyed at 120°C for 60 minutes in the following dye bath adjusted to PH4. Dye bath Sumiacrylic Yellow E-3RD ^*5 2.4%owf Crampons Cachiron Red CD-FGLH ^*6
0.8% owf Basacryl Blue GL ^*7 3.0 owf 6.2 owf Next, the following discharge printing paste was printed and steamed at 120°C for 30 minutes.

[Table] A discharge-printed product with a clear yellow color on a black background was obtained. (Note) Products marked with an asterisk (*) used in the examples are manufactured by the following companies. *1 Mitsui Toatsu Kagaku (KK) *2 Sansho (KK) *3 Sumitomo Chemical (KK) *4 Same as above *5 Same as above *6 Hodogaya Chemical (KK) *7 Verdeitsch Publishing *8 Bayer *9 Meisei Chemical Industrial (KK)

Claims (1)

[Claims] 1. Use of a discharge printing paste containing at least one discharge printing agent selected from the group consisting of sulfinic compounds and stannous compounds and a compound represented by the following general formula (1). Characteristic discharge printing method for polyester textile products. However, R ₁ and R ₂ are H, an alkyl group, halogen R ₃ is a C ₁ to C ₄ alkyl group, or R ₄ is −CH ₂ −CH ₂ −, −CH=CH− −CH ₂ −
CH(OH) - m is 0 or 1 n is 1 to 10 2 The above discharge printing agent is Zn(HSO ₂ H ₂ O) ₂ , ZnSO ₂ ,
The discharge printing method according to claim 1, characterized in that the discharge printing method is selected from CH ₂ O.H ₂ O and SnCl ₂ . 3. The discharge printing method according to claim 1 or 2, wherein the compound represented by the general formula (1) is contained in the discharge printing paste in a proportion of 2 to 10% by weight.