JPS6025555B2 - printing paste - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention particularly relates to a dye printing paste for printing textile products on molded articles that are dyeable with disperse dyes such as polyester, polyamide, and polyacrylonitrile. The present invention relates to a printing paste that does not cause screen clogging and can provide printed products with excellent film strength, uniformity, and sharpness.

Conventionally, when printing polyester products with a printing paste containing a disperse dye thickened with a salt of a cross-linked vinyl polymer containing carboxyl groups, the cross-linking density of the vinyl polymer causes clogging of the screen and sharpness. , a difference can be seen.

That is, in the case of a vinyl polymer with a high crosslinking density, the clogging of the screen was good, but the sharpness was extremely poor, and the pattern could not be faithfully reproduced on the cloth. On the other hand, in the case of a pinyl polymer with a crosslink density of 4, the sharpness is relatively good, but it has the drawback of clogging the screen, so it satisfies both the prevention of screen clogging and the sharpness. The development of thickeners is strongly desired. The inventor of the present invention has arrived at the method of the present invention as a result of intensive research in order to obtain a printing lake that does not clog the screen and has excellent sharpness.

That is, the present invention uses 'a--a salt of a carboxyl group-containing crosslinked vinyl polymer and {b--at least one type of lake agent selected from natural thickening agents and semi-synthetic thickening agents {a):'b}= 95
: 5 to 50:50, and a total of 1.0 to 15% by weight of ta and {b-. Esther from 0.1 to 5. This is a printing paste containing a weight percent of Since the printing paste of the present invention has excellent screen passability, there are no problems such as clogging, and printed products with excellent mold edge sharpness can be obtained. In addition, it has many characteristics such as good color development, uniformity, and build-up properties, as well as excellent de-sizing properties after fixation, so that clear printed products with good texture can be obtained. If a salt of a carboxyl group-containing crosslinked polymer is used alone, unless the crosslinking density is high, the screen passability will be poor and the screen will become clogged, so a low crosslinking density or non-crosslinked type will not be satisfactory from the point of view of continuous operation. Therefore, from the point of view of continuous operation, it is preferable to use one with a relatively high crosslink density, but on the other hand, the higher the crosslink density, the greater the water holding capacity, and the more free water there is, the more likely it is that bleeding due to capillary action will occur. Because the viscosity is significantly increased and the solid content is low, the film layer is thin, and the film itself is hard and brittle, making it difficult to form a uniform and continuous film, which can cause fading during printing and drying. This results in disadvantages such as: In the present invention, by blending a natural thickening agent and/or a semi-synthetic thickening agent with relatively low water-retentivity in a specific proportion, and also using a specific ester-based auxiliary agent, the continuous operation is not impaired.
They also succeeded in obtaining a printing paste with excellent sharpness and no bleeding. The salts of the carboxyl group-containing crosslinked vinyl polymer used in the present invention include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and maleic acid monoester; A polyfunctional monomer having two or more ethylenically unsaturated groups in its molecule that can be copolymerized with an acid and, if desired, other ethylenic monomers that can be further copolymerized with the above unsaturated carboxylic acid and polyfunctional monomer. Examples include salts of crosslinked polyvinylcarboxylic acids obtained by copolymerizing unsaturated monomers (hereinafter referred to as additional unsaturated monomers). Preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, and maleic acid. Polyfunctional monomers that can be used include ethylene glycol diacrylate, ethylene glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, trimethylolpropane di-, tri-acrylate or di-, tri-methacrylate, Di-, tri-, tetra-acrylate or di-, tri-, tetra-methacrylate of bentaerythritol, diacrylate or dimethacrylate of polymethylene glycol, diacrylate or dimethacrylate of polyalkylene ether glycol, erythritol, mannitol, sorbitol Polyhydric alcohols such as polyacrylates or polymethacrylates and ethylenically unsaturated acid polyesters such as brans, ethylene glycol divinyl ether, butanediol divinyl ether, di- or tri-vinyl ether of trimethylolproban, pentaerythritol di-, tri- or tetra-vinyl ethers, polyhydric alcohols such as polyvinyl ethers such as sorbitol, erythritol, mannitol, etc., polyvinyl ethers such as brans, diallyl fumarate, diallyl maleate, etc.
, triallyl trimellitate, diallyl phthalate,
Diallyl isophthalate, dimethallyl phthalate, dimethallyl isotalate, diallyl monohydrogen phosphate, triallyl phosphate, diallyl monomethyl phosphate, diallyl monoethyl phosphate, diallyl monophenyl phosphate, diallyl monobenzyl phosphate, diallyl Polyallyl or polymethallyl esters of organic or inorganic acids such as monohydrogen phosphite, triallyl phosphite, diallyl monomethyl phosphite, diallyl monophenyl phosphite, diallyl monobenzyl phosphite, di- or triallyl ether, di-, tri- or tetra-allyl ether of bentaerythritol, erythritol polyallyl ether, esthritol polymethallyl ether, arapinose polyallyl ether, arabitol polyallyl ether, xyrose polyallyl ether , polyalcohols such as glucose polyallyl ether, mannose polyallyl ether, mannitol polyallyl ether, sorbitol polyallyl ether, inositol polyallyl ether, low-sugar polyallyl ether, and polyallyl such as bran. or polymethallyl ethers, polyunsaturated acid amides such as methylenebisacrylamide, methylenebismethacrylamide, ethylenebisacrylamide, ethylenebismethacrylamide, dihydroxyethylenepisacrylamide, tris(acryloyl)hexahydro S-triazine. and divinyl ketone. However, particularly preferred are polyvinyl ethers and polyallyl ethers such as polyhydric alcohols and brans. Additional unsaturated monomers that can be used include acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate, and stearyl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylhexyl methacrylate, and hydroxyethyl methacrylate. rate,
Methacrylic acid esters such as hydroxypropyl methacrylate, dimethylaminoethyl acrylate, t-butylamide/ethyl methacrylate, cyclohexyl methacrylate, glycidyl methacrylate, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, methyl vinyl esters, etc. ether, vinyl ethers such as isobutyl vinyl ether, acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, N-alkoxymethylacrylamide, N-hydroxyethylacrylamide, itaconic acid In addition to unsaturated acid amides such as amide and diacetone acrylamide, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, styrene, vinylpyrrolidone, ethylene, propylene, isobutylene, butadiene, dimethyl maleate, allyl glycidyl ether , diglycidyl maleate and the like.

The copolymerization ratio of the unsaturated carboxylic acid, polyfunctional monomer, and additional unsaturated monomer is usually 40 to 99.
99:0.01-15:0-59.99 is preferable, and 60-99.5:0.5-10:0-39.5 is particularly preferable. Alternatively, a carboxyl group-containing linear polymer may be crosslinked to the same degree of crosslinking density by post-treatment. The carboxyl group-containing crosslinked polymer is neutralized with an alkali by hanging and used as a salt such as sodium salt, potassium salt, ammonium salt, or amine salt.

On the other hand, as disclosed in JP-A No. 52-127998, an unsaturated carboxylic acid or an additional unsaturated monomer mainly composed of the unsaturated carboxylic acid and a polyfunctional monomer are mixed in a water-soluble organic solvent. The polymerization may be carried out while the alkali is added, and at the same time, the alkali may be sequentially added to carry out the polymerization and neutralization in parallel. In addition, natural thickening agents and semi-synthetic thickening agents to be blended with the salt of the cross-linked polymer include cellulose derivatives such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylhydroxyethylcellulose, and carboxymethylcellulose, locust pea gum type, Examples include natural thickening agents (including lake additives) such as guar gum type and sodium alginate, and semi-synthetic thickening agents. 5 measured in °C
The viscosity of the aqueous solution is less than 1000PS, especially 300% by weight.
Among these, carboxymethyl cellulose, locust bean gum, and guar gum are particularly preferred.

The weight ratio of the salt of the crosslinked polymer and the natural or semi-synthetic sizing agent is 95/5 to 50/5, preferably 8
It is 0/20 to 60/40. The salt of the crosslinked polymer and the natural or semi-synthetic thickening agent may each be used alone in the preparation of a printing paste as an aqueous solution, or they may be mixed and used after being dissolved in water. The total amount used is 1.0 to 15% by weight based on the printing paste. The disperse dye used in the present invention may be a powder product or a liquid product.
The nonionic aqueous preparation described in JP 1-100125 may also be used. As the ester of polyalkylene glycol and organic carboxylic acid used in the present invention, a compound represented by the following formula (1) is particularly preferable.

Here, R,,R2: carbon number is 1 to 30, preferably 4 to
22 alkyl group, aralkyl group, etc. R3: hydrogen or lower alkyl group R4: lower alkylene group m: positive integer, n: 0 or a positive integer, m10n>50, m>n.

Particularly preferable examples of the specific compound represented by the above formula (1) include polyethylene glycol, polypropylene glycol, polyethylene glycol/polypropylene glycol block copolymer, ethylene oxide/propylene oxide random copolymer, and polyethylene glycol/polytetramethylene glycol. Block copolymer, 2
Examples include fatty acid esters of polyalkylene glycols such as alcohol/alkylene oxide adducts.

Examples of compounds other than formula (1) include di, tri, and tetraesters of alkylene oxide conductors and organic monocarboxylic acids, such as polyhydric alcohol/alkylene oxide adducts and polyhydric carboxylic acid/alkylene oxide adducts. Ru.

The blending amount is usually 0.1 to 5. % by weight, preferably 0.2 to 3. % by weight. Furthermore, even better results can be obtained by using sulfated oil such as funnel oil in an amount of about 0.1 to 2% by weight based on the printing paste. In order to improve stability, the printing paste may further contain a conventional reduction inhibitor, a nonvolatile organic acid such as malic acid, and a conventional deep dyeing agent. The present invention will be explained below with reference to Examples.

Note that parts and percentages in the examples are parts by weight and percentages by weight. Example 1 An autoclave was charged with 45.5k9 of methyl alcohol, and 0.08k9 of penzoyl peroxide was dissolved therein.

On the other hand, a mixed monomer of 16 kg of acrylic acid and 0.24 kg of glycerin triallyl ether and 18.5 k9 of a 48% sodium hydroxide aqueous solution were prepared, divided into 28 portions, and poured into the methyl alcohol at 65° C. at 15 minute intervals. The polymerization reaction was completed in 1 hour by repeating the neutralization polymerization. Cross-linked sodium polyacrylate is formed in the form of a slurry, and this slurry is passed through a furnace to remove methyl alcohol.
After drying, a white fine powder was obtained. 3 parts of the obtained fine powder, Fine Gum SP-1 (Daiichi Kogyo Seiyaku Co., Ltd., carboxyl methyl cellulose, 5% aqueous solution viscosity 10 or less) 0.5
0.2 parts of malic acid, 0.2 parts of sodium metanitrobenzenesulfonate and 1 part of water were added to make the whole into 10 base parts to form a base paste.

This base glue 8 woven polyethylene glycol (EO130
0.3 parts of molar distearate, 5 parts of Dyanix Blue BG-FS Liquid (Mitsubishi Kasei Co., Ltd., disperse dye), and 14.7 parts of water were added and mixed thoroughly to form a colored paste. The viscosity of the colored paste is 1120 PS (Tokyo Keiki B Mother's day type viscometer rotor #
7.5 enemies. p. m, 25 qo). A 135 mesh pongee line pattern was printed on polyester georgette using the above color paste using a flat screen printing machine, and dried.
After high-temperature steaming at 17,000 for 1 minute, reduction cleaning was carried out at 80,000 for 5 minutes in a conventional manner.

As a result, a pattern with excellent sharpness was reproduced, and the color paste passed through the screen very well.

Examples 2 to 6 and Comparative Examples 1 to 2 A colored paste with the following formulation was prepared with the composition and concentration shown in Table 1, and it was printed on polyester georgette in the same manner as in Example 1, dried, and steamed at high temperature. , reduced cleaning.

The results are shown in Table-1. Colored glue prescription glue Composition and amount shown in Table 1 Dianics Blue BG1F
S Liquid 5 parts Malic acid 0.2 parts Thorium metanitrobenzenesulfonate ○-2 parts Polyethylene glycol (EO 130 mol) Distearate 0-$ parts Table-I1
) Polymer synthesized in Example 1 2) Daiichi Kogyo Seiyaku Co., Ltd., Carboquine Methylcellulose 3)
×: Poor △: Slightly poor ○: Good As is clear from Table 1, it is not until polyalkylene glycol gester is added to the printing paste, which is a combination of cross-linked polyacrylate and semi-synthetic paste in a specific ratio, that the screen is screened. A printing paste with good permeability was obtained, and a printed product with excellent sharpness was obtained.

Comparative Example 3 In Example 6, when the colored paste excluding polyethylene glycol distearate was adjusted, the viscosity was 1
At 0500, a target color paste was obtained.

Using this colored paste, printing was carried out on polyester georgette in the same manner as in Example 1, followed by drying, high-temperature steaming, and reduction cleaning. As a result, the obtained printed product was significantly inferior in sharpness compared to Example 6. Example 7 and Comparative Examples 4 to 12 Crosslinked sodium polyacrylate 2 used in Example 1
．． A base glue consisting of 4% Fine Gum SP-10.6% and 0.5% of various surfactants shown in Table 2 was prepared.

Add an appropriate amount of base glue to 5 parts of Dianex Blue BG-FS Liquid, and make the total amount to 10 parts with water to make the color paste viscosity 9000 ~
I adjusted the PS color paste to 1200. Using this colored paste, in the same manner as in Example 1, lacquer was applied onto polyester georgette, followed by drying, high-temperature steaming, and reduction cleaning. It is shown in Table-2. Table-2 1) Polyethylene glycol/polypropylene glycol copolymer (EO:PO=5:1 mol, number of moles added to alkylene oquinde 100 mol) distearate 2) ○: Good △: Fairly poor ×: Poor ×× : Extremely poor As is clear from Table 2, all of the samples other than the polyalkylene glycol gester of the present invention had poor sharpness.

Example 8 Crosslinked poly(IJ) sodium phosphate 2 used in Example 1
．． 4%, Indaruka PA-30 (Chugai Boeki Co., Ltd., guar gum) 0.6% and polyethylene glycol (EOIO
A base glue consisting of 0.3% of mol) distearate was prepared.

Next, 5 parts of Dianex Flu 8G-FS Liquid,
Adjust the color paste consisting of 8 parts of the above-mentioned lake and 15 parts of water,
Printing was carried out in the same manner as in Example 1 on polyester suede.

As a result, the pattern of the obtained printed product was sharp and uniform. Comparative Example 13 Color paste was adjusted and printed in the same manner as in Example 8 except that polyethylene glycol distearate was not used.

As a result, the pattern of the obtained printed product had significant bleeding,
It was unclear and lacked sharpness. Comparative Example 14 Crosslinked sodium polyacrylate 1 used in Example 1
．． A base glue consisting of 25% and 1.25% of Poval 217 (manufactured by Kuraray, polyvinyl alcohol) was prepared.

Next, 5 parts of Dianex Blue BG-FS Liquid,
8 parts of the above base paste and 15 parts of water were added to form a colored paste.

This colored paste was printed on polyester suede in the same manner as in Example 1.

The colored paste was not only highly viscous and could not produce sufficiently uniform ink lacquer, but also had poor sharpness and desizing properties, resulting in printed fabrics that were unclear and had a hard texture. Example 9 5 parts of mineral oil pen, 5 parts of liquid paraffin, 17 parts of monoethanolamine, 5 parts of sorbitan monolaurate,
In an emulsified dispersion consisting of 805 parts of Sorgen TW and 56 parts of water, 98% of acrylic acid was added. 17 parts of a crosslinked carboxyl group-containing copolymer fine powder consisting of 1 part of Moribe's methacrylic acid and 0.8 parts of erythritol triacrylate was added in small amounts to form a uniform paste.

Above paste 14. $ part, Indaruka PA-3 0.6
part, sodium metanitrobenzenesulfonate 0.2 parts, malic acid 0.2 parts, polypropylene glycol (P0
A colored paste was prepared consisting of 0.2 parts of 70 mol) distearate and 84.5 parts of water.

When printing was performed using this colored paste in the same manner as in Example 1, a printed product with excellent sharpness was obtained.

Claims (1)

[Scope of Claims] 1 (a) a salt of a carboxyl group-containing crosslinked vinyl polymer; and (b) at least one type of sizing agent selected from natural sizing agents and semi-synthetic sizing agents; b) = 95:5 to 50:5
0 weight proportion, and the sum of (a) and (b) is 1.0
The molecular weight is 2000 for printing paste containing ~15% by weight.
A printing paste characterized by containing 0.1 to 5.0% by weight of the ester of the above polyalkylene glycol and organic carboxylic acid. 2 Ester is polyethylene glycol and carbon number 4-2
The printing paste according to claim 1, which is a diester of aliphatic monocarboxylic acid No. 2. 3. The printing paste according to claim 1, wherein (a):(b) is 80:20 to 60:40. 4. The printing paste according to claim 1, wherein the sizing agent selected from natural sizing agents and semi-synthetic sizing agents is carboxymethyl cellulose, locust bean gum type, or guar gum type.