JPH02104776A - Paste for printing - Google Patents

Abstract

PURPOSE:To provide a paste for printing with direct, acid, vat or disperse dye, affording level dyeability and brightness, good in desizing nature, comprising an alkali metal salt of carboxymethylated starch lees having degree of substitution not less than a specified value. CONSTITUTION:The objective paste comprising carboxymethylated starch lees >=0.5 in mean degree of substitution on a pure component basis, prepared by carboxymethylation, using e.g., monochloroacetic acid, of starch such as from (sweet) potatoes. Application of this paste as base paste in printing with direct dye, acid dye, vat dye, disperse dye or naphthol dye will remove drawbacks of conventional paste compositions and give good level dyeing, brightness and desizing performances, thus enabling single use.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a paste for textile printing.

[Conventional technology]

As a printing paste, a natural or synthetic water-soluble polymer compound which is an amorphous solid, dissolves in colloidal form in water, and has a high viscosity at a relatively low concentration is used, and is also called a one-component paste. be. Printing paste is a printing medium that requires shape retention performance to keep the design fixed on the 41 ground and faithfully reproduce the color image on the fabric. Generally, sizing agents are mixed with dyes, acids, alkalis, anti-reduction agents, etc. to form colored pastes, which are used in printing. When using a sizing agent as a printing medium, there are many basic requirements such as water solubility, heating stability, viscosity stability, mechanical stirring stability, acid and alkali resistance, reducing properties, and antibacterial properties. do. The adhesive also plays an important role as a factor that influences various performances after printing on fabric, such as the reproducibility of the image, surface color development, level dyeing, sharpness, and desizing properties. Conventional thickening agents for textile printing mainly include starch or its derivatives, sodium aluminate, tamz derivatives represented by carboxymethyl cellulose (CMC), and natural gums such as galactomannan. Used accordingly. On the other hand, starch meal is a complex mixture whose main components are starch and M-Chengye. For example, in the case of sweet potato starch meal, starch 54
．． 4%, braided fiber, 1fi18.6%, residual ash, crude protein, etc. [Starch Chemistry Handbook 1 Published by Asakura Shoten (1976), p. 361, supervised by Nikoku Nibu, Bareishi, and about starch cake, edited by Futata Nibu, Starch Handbook J Published by Asakura Shoten (1971)
[See page 477 of 1952] As described above, since starch cake is a complex mixture, it has not been known so far that it can be used industrially as a carboxymethyl etherified salt in a printing paste. For this reason, it is currently only used as an inexpensive feed.

Issue 8 to be Solved by the Invention The present inventors have discovered the above-mentioned current situation regarding conventional sizing agents and the fact that the use of starch meal is economically advantageous and that its main components are starch and cellulose. It has been discovered that by carboxymethylating starch residue, it can be effectively used as a printing paste in general mechanical printing.

[Means to solve the problem]

The present invention covers direct dyes, M dyes, architectural dyes, disperse dyes,
As a printing sizing agent for naphthol dye 1, rapitogen dye, or vat dye, the average degree of substitution in terms of purity is 0.
The present invention provides a printing paste characterized by containing as an essential component an alkali metal salt of carboxymethylated starch lees having a molecular weight of 5 or more. The starch meal in the present invention is preferably an inexpensive fibrous starch meal originating from sweet potatoes, potatoes, arrowroot, etc., but starch meal derived from grains such as corn, rice, wheat, barley, etc. can also be used. Carboxymethylation of starch meal is usually carried out in the same way as in the production of carboxymethyl cellulose and carboxymethyl starch.
An alkali (especially caustic soda) is applied, and monochloroacetic acid or monochlorosodium acetate is added to form an ether bond. In this case, if the polysaccharide is cellulose, the degree of etherification is theoretically 3.0, that is, all three hydroxyl groups per unit of anhydroglucose can be etherified, but this etherification is The degree of substitution calculated as an average molecular weight of 162 with three hydroxyl groups is calculated as the average degree of substitution in terms of purity (
101). In the present invention, the average degree of substitution of the alkali metal salt in the carboxymethylated starch meal is 0.5 or more in terms of purity, and when the degree of substitution is less than 0.5, it is water-soluble as a printing paste and The size removal property is insufficient, and the object of the present invention cannot be achieved. When using the alkali metal salt of carboxymethylated starch residue as a printing paste, substances other than starch and cellulose and water-insoluble substances may cause clogging of the screen mesh.
It must be removed as much as possible. Therefore, after carboxymethylation of the starch meal, it is necessary to remove water-insoluble substances using a centrifuge, or to grind the starch meal finer than the usual screen mesh during the final grinding. The printing paste of the present invention includes direct dyes, Wi-based dyes, architectural dyes, disperse dyes, naphthol dyes, rapitogen dyes,
It can be used as a printing medium when preparing color pastes made of vat dyes and pigments. In addition, when applying color paste to various textile materials using these dyes, various acids such as citric acid, tartaric acid, malic acid, acetic acid, etc. are used in combination for the purpose of adjusting the pH of the color paste. In addition to organic acids, reduction inhibitors such as sodium chlorate and sodium m-nitrobenzenesulfonate, salts such as ammonium sulfate and ammonium tartrate, and urea, dye dissolvers, antifoaming agents, penetrants, 1M dyes, and leveling agents. There is no problem in using various auxiliary agents suitable for printing processing, such as deep dyeing agents, moisture absorbers, and humectants. In addition, the printing paste of the present invention exhibits sufficient basic performance and printing effect even when used alone as a printing medium, but various thickening agents conventionally used, such as starch, modified starch, Natural gum, sodium alginate or each! ! Since compatibility with carboxymethylcellulose having a conversion of 21 degrees does not pose a problem, it is also possible to use it in combination with these to form a printing medium. Next, the present invention will be specifically explained using examples. [% and parts are based on weight] Example 1 500 g of dried sweet potato starch meal and dried corn starch meal (81% i containing 13 types) were placed in a single-screw five-pronged blender.
Add a solution of a prescribed amount of sodium hydroxide (shown in Table 1) in 1 ooog of 50% methanol,
The mixture was stirred and mixed at 0°C for 60 minutes. Next, a solution of a predetermined amount of monochloroacetic acid (shown in Table 1) dissolved in an equal amount of 90% methanol was added dropwise over 60 minutes, and the mixture was heated to approximately 40°C! After mixing for 0 minutes, 65℃
The etherification reaction was carried out at the same temperature for 2 hours. After the etherification was completed, the reaction solution was cooled and neutralized with acetic acid. Add 2500g of 70% methanol to this neutralized solution and
After stirring for a minute, the mixture was centrifuged, subjected to solid-liquid separation, and the solid portion was dried and ground. As a result, carboxymethylated sweet potato starch meal and corn starch meal having the analytical values shown in Table 1 were obtained. Example 2 The following base glue was prepared by appropriately selecting from the sample η) obtained in Example 1. Original glue No. I Potato starch Shogashiwa Motonori 9%2 C
M-made potato V powder Shogaku Motonori 15% 3 CM-made potato starch Shogaku Motonori 10% 4 CM-made corn made into Matsusaku ■ Gennori 8% 5 CM-made corn starch lees ■
Motonori 17% 6 Commercial corn V powder Matsukashiwa Φ Motonori 2
2% Polyester Ten I under the following color glue conditions for each base glue
Screen printing was performed on the fabric using a disperse dye. Test In: Polyester twill colored glue formulation: KAYALON POLYESTERBLUE2R-
SF (PASTE) (Nippon Kayaku Co., Ltd., disperse dyeing $4) 3% citric acid 0.3% base paste 60% water
Appropriate amount Color paste viscosity 10,000±500cps (BH type RNo. 5
．． 2Orpm, 25℃) Printing process: Flat screen printing +, - drying → high temperature steamer (135mesh) (HTS
) - Water washing - Reduction soaping - Water washing -> drying The results of printing suitability for disperse dyes are shown in Table 2. Example 3 In the same manner as in Example 2, an aqueous solution of base glue with a predetermined concentration was prepared using the CM-converted potato starch Shobaku ~ ■ and the CM-converted corn starch Shogashiwa ~ ■ obtained in Example 1, and the following color paste conditions were applied. Screen printing was performed using a resistant dye on a nylon 11m cloth. Sample fabric: Nylon Color glue prescription: ON FAST NAVY BLUE R (
Manufactured by Bayer Japan, acidic! J! 0.5% ammonium tartrate 0.3% carazol TG 1.0% base paste
60.0% water
Appropriate amount Color paste viscosity: 8.000±500cps (BH54RNo, 5.2 Or pm, 25℃) Print on nylon cloth using a pattern pattern using a 135 mesh screen, and after preliminary dry explosion, use a high pressure steamer (HTS).
Washed with water and soaped using heat transmission. Table 3 shows the results of printability with acid dyes. Example 4 An aqueous solution of base glue of a predetermined concentration was prepared using the commercialized potato starch Shobaku~@ and the commercialized corn starch Shobaku~■ of Example 2, and dyeing was applied directly to cotton fiber cloth under the following color paste conditions. Screen printing was performed using Sample 4j: Cotton satin colored glue prescription: KAYARUS 5UPRA BLUE BCL
(manufactured by Nikki Kaisha, direct dye) 296 Carazol TK 5% urea
・2% base glue
60% boiling water
Appropriate amount Color paste viscosity: a, ooo±500cps (BH type RNo, 5.2Orpm, 25℃) Cotton satin 4
1 was printed using a pattern pattern using a 100 mesh screen, and after preliminary drying, it was steamed with normal pressure saturated steam, washed with water, and soaped. Table 4 shows the printability results for direct dyes.

【Effect of the invention】

When the printing paste of the present invention is applied as a printing medium, the basic requirements are water solubility, heat stability, oral viscosity stability, mechanical stirring stability, f) IS, alkali resistance, and ITF.
In addition to eliminating the deficiencies of various conventionally used glue compositions in terms of chemical properties, antibacterial properties, reduction resistance, compatibility, etc., it also has a certain surface coloring property that depends on appropriate fluidity. Excellent level dyeing and sharpness are expressed on the fabric, and at the same time, size removal properties are also improved. Because of these properties, the sizing agent of the present invention can be used alone as a printing medium, and furthermore, starch residue can be used effectively.Patent applicant: Dai-ichi Kogyo Seiyaku Co., Ltd.

Claims (1)

[Claims] An alkali of carboxymethylated starch residue with an average degree of substitution of 0.5 or more in terms of purity, as a printing sizing agent for direct dyes, acid dyes, vat dyes, disperse dyes, naphthol dyes, rapitogen dyes, or vat dyes. A printing paste characterized by containing a metal salt as an essential component.