JPS6317155B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a discharge printing aid. More specifically, it relates to a dyeing aid for white or colored discharge printing used for polyester fiber materials and triacetate fiber materials. Discharge printing has many advantages such as the back side of the fabric is also dyed in the ground color, the ground color is deep, a delicate pattern with no pattern deviation can be obtained, and there is no boundary line between areas, making it a traditional high-quality printing technology. It has been applied to various fiber materials since then, but no satisfactory effect has been obtained despite technical studies on discharge printing of polyester fiber materials and triacetate fiber materials for a long time. Ground dyeing methods include high temperature dyeing method, carrier dyeing method, dye dipping method (padding method), etc. High-temperature dyeing methods can produce strong, deeply dyed products, but discharge printing is difficult. The carrier dyeing method has many troubles in the work and dyeing process.
With the dye dipping method, discharge printing is relatively easy, but the dyeing performance is poor, and the rate of failure is high because discharge printing and fixation of the ground dye are performed at the same time. Although each of the above-mentioned various dyeing methods has problems, the high-temperature dyeing method is widely used. As the discharge printing agent, sulfine compounds such as zinc diformaldehyde sulfoxylate are often used for white discharge printing, and stannous chloride is often used for colored discharge printing. In place of stannous chloride, stannous compounds such as stannous phosphate, acidic stannous phosphate, stannous oxalate, stannous acetate, and stannous fluoride may be used. When discharging polyester fiber materials that have been background-dyed using a high-temperature dyeing method, sulfinic compounds and stannous compounds are effective as discharging agents, but they are often insufficient in discharging effect alone, and are usually In order to enhance the discharge printing effect, a compound that has a discharge printing promoting effect (discharge printing auxiliary agent) is used in combination. Conventionally, this compound is a derivative of diphenyl or phenol, especially P-phenylphenol, P-phenylphenol,
-Phenylphenol alkylene oxide adducts and alkylene oxide adducts of aromatic monocarboxylic acids have been used. These compounds still have insufficient discharge printing promotion effect. Diphenyl and phenol derivatives also have the problem of remaining in the fibers and greatly reducing the light fastness of the accent color. The present inventors have studied to obtain a discharge printing aid that does not cause such problems when discharging polyester and triacetate fiber materials.
We have arrived at the present invention. That is, the present invention has the general formula X ¹ -O(-AO)- _o X ² ...( ₁ ) (wherein,
They are an aralkyl group, an aralkenyl group, an aralkyl-substituted aryl group, an OH-substituted aryl group, or an aromatic acyl group. X ² is an aromatic acyl group.
A is an ethylene group and a propylene group. n is an integer from 1 to 10. ) is a discharge printing auxiliary agent consisting of a compound represented by: Examples of the above aryl groups include aryl groups (such as phenyl groups) and alkaryl groups.

[Formula] R: alkyl group having 1 to 20 carbon atoms, m: 1 to 3, nonylphenyl group, etc.),
Aralkyl group

[Formula], etc.), Ararque Nyl group (

[Formula], etc.) aralkyl-substituted aryl group (

【formula】

[Formula] q: 1 to 3, etc.), as the OH-substituted aromatic hydrocarbon group, for example, an OH-substituted aryl group

[Formula] (p: 1-3), etc. In addition, as an aromatic acyl group,

【formula】

【formula】 (r: 1, 2, etc.);

【formula】

Examples include [Formula] (s: 1-3). The above X ₁ and X ₂ may be the same or different. Among X ₁ and X ₂ , preferred is an aromatic acyl group, and particularly preferred is

[Formula]. Further, A is an alkylene group or a substituted alkylene group. Examples of the alkylene group include alkylene groups having 2 to 4 carbon atoms such as ethylene, propylene, and butylene, and examples of the substituted alkylene group include styrene. One or more types of groups (random or block type) are used for these. Among these, preferred are ethylene group,
Among them, a propylene group and a combination group of an ethylene group and a propylene group, and an ethylene group is particularly preferred. n is an integer of 1 to 10, preferably an integer of 1 to 5. If n is larger than 10, the discharge printing effect will be insufficient, and in the case of white discharge printing, the brightness will decrease, and in the case of colored discharge printing, the hue will become unclear. The specific compounds represented by general formula (1) are as follows. 1 Aromatic carboxylic acid diester of (poly)alkylene glycol 2 Aromatic carboxylic acid monoester of (poly)alkylene glycol Aromatic alcohol (or phenol) monoether The compound represented by general formula (1) can be produced by known esterification and etherification reactions. For example, (1) a method of esterifying (poly)alkylene glycol and an aromatic monocarboxylic acid (lower ester) (transesterification reaction); (2)
Adding alkylene oxide to aromatic monocarboxylic acid and etherifying it with aromatic alcohol or phenols (reacting with CH ₃ ONa etc. to generate OH)
(3) method of adding alkylene oxide to phenols or aromatic alcohol and esterifying it with aromatic monocarboxylic acid (lower ester) (transesterification reaction), (4) A method of adding an alkylene oxide to an aromatic monocarboxylic acid and esterifying it (transesterification) with an aromatic monocarboxylic acid (lower ester). A preferred method is method (1). The auxiliary agent of the present invention can be applied to polyester fiber materials and triacetate fiber materials. The polyester fibers mentioned above include polyester fibers (for example, polyethylene terephthalate fibers) and other fibers (for example, cotton, wool, rayon,
Mixed fibers with acrylic, nylon, acetate) are recommended. Examples of triacetate fibers include triacetate fibers (all three hydroxyl groups of cellulose are replaced with acetic acid groups) and mixed fibers of this and other fibers (e.g., cotton, wool, rayon, acrylic, nylon, diacetate, polyester). can be given. Examples of polyester fiber materials and triacetate fiber materials include knitted fabrics of these fibers. In all of these, excellent discharge printing effects can be obtained using the present technology. When performing discharge printing using the auxiliary agent of the present invention, the auxiliary agent is blended or added to a commonly used discharge printing paste solution. The amount of the auxiliary agent added in the present invention is usually 0.5 to 15% by weight, preferably 2% by weight, based on the aqueous sizing solution.
~10%. An example of the formulation of the discharge printing paste containing the auxiliary agent of the present invention is as follows. Formulation Example 1 (White discharge printing) Original paste or aqueous size solution usually 50 to 70% by weight (usually 5 to 15% by weight aqueous size solution) Sulfinic discharge dye usually 2 to 10% by weight Auxiliary agent of the present invention 〃0.5 to 15 〃 Other drugs 〃 0.05-20 〃 Water Remaining 〃 Prescription example 2 (Colored discharge printing) Base glue or size agent aqueous solution Usually 50-70% by weight (Usually 5-15% by weight aqueous size solution) Stannous-based discharge printing agent 〃 2-15 〃 Non-removable dye 〃 0.05-10 〃 Auxiliary agent of the present invention 〃 0.5-15 〃 Other chemicals 〃 0.05-20 〃 Water Residual dyes that are weak against reduction (removable) are suitable as dyes for ground dyeing such textile materials. It is preferable to select a dye that is resistant to reduction (a non-dischargeable dye) for the accent color during color discharge printing. Examples of removable dyes include azo disperse dyes. Examples of non-removable dyes include quinone-based disperse dyes and blended dyes of quinone-based disperse dyes and acid dyes, reactive dyes, direct dyes, and the like. Examples of the sizing agent components used in the base glue include highly etherified locust bean gum, crystal gum, fritish gum, and the like. Examples of sulfin-based discharge printing agents include sodium bisulfite and zinc hyposulfite formalin hydrate. The stannous discharge printing agent includes stannous chloride, stannous phosphate, acidic stannous phosphate, stannous oxalate, stannous acetate, and stannous fluoride (preferably stannous chloride). can give. Other agents include antifoaming agents (octyl alcohol, tributyl phosphate, silicone emulsion, etc.), moisture absorbers (urea, polyethylene glycol, etc.), and tin-scorch inhibitors (hexamethylene diamine, etc.). When performing textile printing using the above-mentioned discharge printing paste, a normal method is used. In other words, the above-mentioned discharge printing paste is printed on the ground-dyed fabric that has been dyed and fixed with a removable dye (a dye that is weak against reduction) using a high-temperature dyeing method, etc. After drying, the decolorization of the ground-dye dye and the fixation of the non-removable dye are carried out in a steaming process. Do it at the same time. The printing method may be any conventional method, and typical methods include screen printing, rotary screen printing, roll printing, and the like. Drying is performed, for example, at 100° C. for 1 to 5 minutes. Examples of fixing methods include normal pressure high temperature steaming method, high pressure steaming method, and thermosol method.
After fixing, wash with water, remove glue, and then soap.
Further wash with water and dry. When the auxiliary agent of the present invention is used for discharge printing, the printed material shows clear removal of the removable dye, excellent color development of the accent color, little halation, and good light fastness. be. The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Parts and percentages in the examples are by weight. Example 1 (1) Auxiliary agents of the present invention [the following () to (X)] (2) Ground dyeing recipe (hue: black) Sample fabric: Polyester Ponzi dyeing method: High temperature dyeing, 130°C x 60 minutes Auxiliary agent Ion Net RAP-50 (manufactured by Sanyo Kasei) 0.5g/l Dye: Miketon polyester dyeing method GiBlue R (manufactured by Mitsui Toatsu) 3% ow Diamondx Yellow G-FS (manufactured by Mitsubishi Kasei) 1.5% ow Sumikalon Red S-BL (manufactured by Sumitomo Chemical) 0.5% ow (3) Discharge paste liquid formulation (i) White Base paste for discharge printing 50 parts Decroline Soluble Conc 20 (Sulfin-based discharge dye manufactured by BASF) Urea 3 Auxiliary agent for discharge printing and dyeing 5 Water Remaining amount total 100 parts (ii) Base paste for coloring and discharge printing Note 1 50 parts Dye Note 2 2 Stannous chloride 5 Urea 3 Discharge dyeing aid 5 Water Remaining amount Total 100 copies Note 1 Aqueous solution containing 12% of original glue Sorbitose PAN (manufactured by Skorten) Note 2 Dye (a) Diamonds Blue BG-FS ( (manufactured by Mitsubishi Kasei) (b) Diamond thread BN-SE (manufactured by Mitsubishi Kasei) (4) Processing process Ground dyeing - Discharge printing - Paste stamping - Drying - Steaming - Washing - 100
℃ x 3 minutes HT-S method 170℃ x 10 minutes Note 3 Reduction cleaning - water washing - drying - finishing Note 3 Reduction cleaning "Ionetsu RK-15" (manufactured by Sanyo Chemical) 1g/l Hydrosulfite 1g/l Caustic soda 1g/ l 80℃×5 minutes (5) Evaluation results

【table】

[Table] The brightness of the ground-dyed sample cloth is set to 0%.

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1 General formula X ¹ -O-(AO)- _o X ² (1) (wherein, X ₁ is an aryl group, an alkaryl group
They are an aralkyl group, an aralkenyl group, an aralkyl-substituted aryl group, an OH-substituted aryl group, or an aromatic acyl group. X ² is an aromatic acyl group.
A is an ethylene group or a propylene group. n is an integer from 1 to 10. ) A discharge printing aid consisting of the compound shown in