JPH0248674B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a paste for stamping. As a printing paste, a natural or semi-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 base paste. It is. Printing pastes are printing media that are required to have shape-retaining properties to keep designs fixed on fabrics and faithfully reproduce color images on fabrics. Generally, a size agent is mixed with a dye, an acid, an alkali, a reduction inhibitor, etc. to form a colored paste, and this is used in the printing process. When using a sizing agent as a printing medium, water-soluble,
Heating stability, viscosity stability over time, mechanical stirring stability,
There are many basic requirements such as acid/alkali resistance, salt resistance, antibacterial properties, reduction resistance, and compatibility. The adhesive also plays an important role as a factor that affects various performances such as the reproducibility of the image expressed after printing on the cloth, surface coloring, level dyeing, sharpness, and desizing properties. Conventionally, sizing agents have mainly been starch or its derivatives, sodium alginate, cellulose derivatives such as carboxymethyl cellulose (CMC),
There are natural gums such as galactomannan, which are used depending on the purpose of printing. On the other hand, rice bran is used in small amounts in paper pattern printing, etc., and its purpose is to adjust the viscosity of rice bran paste and increase the bulk of the paste. This rice bran could not be used for general mechanical printing because of its poor solubility and fluidity, as well as the presence of many impurities such as crude protein and fats and oils. In addition, defatted rice bran, or rice bran lees, is a large amount of by-product when extracting rice bran oil from rice bran, but it has almost no effective use other than adding less than 10% to the feed as a compound feed. Ta. The present inventors focused on the above-mentioned current situation regarding conventional thickeners and the fact that the use of rice bran is economically advantageous and its main component is polysaccharide, and by carboxymethylating rice bran. It was discovered that it can be effectively used as a printing paste not only for pattern printing but also for general mechanical printing. The printing paste according to the present invention contains as an essential component an alkali metal salt of carboxymethylated rice bran having an average degree of substitution in terms of purity of 0.3 or more. In the present invention, rice bran includes defatted rice bran, that is, rice bran lees. Rice bran is a mixed powder produced when brown rice is polished, and its main component is polysaccharides. In addition, defatted rice bran is the residue obtained by extracting rice bran oil from rice bran. Carboxymethylation of rice bran is usually carried out by CMC or
Similar to the production of CMS, rice bran is treated with alkali (especially caustic soda), and monochloroacetic acid or monochlorosodium acetate is added to form ether bonds. 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; The degree of substitution calculated assuming a certain average molecular weight of 155 is referred to as the average degree of substitution ( ) in terms of purity.
In the present invention, the average degree of substitution of the alkali metal salt in carboxymethylated rice bran is 0.3 or more;
If it is less than 20%, water solubility and desizing properties as a printing paste are insufficient. In addition, when used as a reactive dye, the average degree of substitution must be 0.7 or more, and if the degree of substitution is less than 0.7, it becomes impossible to use in terms of gelation and desizing properties of colored paste. In general, reactive dyes dye by chemically bonding with the hydroxyl groups of cellulose fibers through reactive groups such as chlorinated triazine and vinyl sulfonic acid present in their molecules, so they naturally bond with printing pastes that have hydroxyl groups. there's a possibility that. Such bonding depends on the presence or absence of primary hydroxyl groups in the glue that easily react with reactive dyes, so if the average degree of substitution is set to 0.7 or more in order to extremely substitute the primary hydroxyl groups, bonding with reactive dyes will occur. becomes smaller and can be used as a paste for textile printing. When using an alkali metal salt of carboxymethylated rice bran as a printing paste, substances other than polysaccharides and water-insoluble substances must be removed as much as possible because they cause clogging of the screen mesh. Therefore, after carboxymethylation of rice bran, it is necessary to remove insoluble matter using a centrifuge or to grind the rice bran finer than a normal screen mesh during final grinding. The sizing agent of the present invention can be used in the preparation of colored pastes consisting of direct dyes, acid dyes, vat dyes, disperse dyes, naphthol dyes, labidogen dyes, vat dyes, metal complex dyes, pigments, and reactive dyes (0.7 or higher). It is applicable as a printing medium. In addition, when adjusting color pastes for various textile materials using these dyes, various acids such as citric acid, tartaric acid,
Organic acids such as malic acid and acetic acid used for the purpose of adjusting the pH of color paste; reduction inhibitors such as sodium chlorate and sodium m-nitrobenzenesulfonate;
In addition to salts such as ammonium sulfate and ammonium tartrate and urea, we also use dye dissolving agents, antifoaming agents, penetrating agents, slow dyeing agents, level dyeing agents, deep dyeing agents, hygroscopic agents, humectants, etc. for various printing processes. There is no problem even if other adjuvants are used together. Although the printing paste according to the present invention has sufficient basic performance and printing effect even when used alone as a printing medium, it can be used with various pasting pastes such as starch, modified starch, natural gum, and sodium alginate. Furthermore, since it is compatible with carboxymethyl cellulose having various degrees of substitution, it is also possible to use these in combination to form a printing medium. When applying the size agent of the present invention as a printing medium,
Disadvantages of rice bran regarding basic requirements such as water solubility, heating stability, viscosity stability over time, mechanical stirring stability, acid/alkali resistance, chemical resistance, antibacterial property, reduction resistance, compatibility, etc. In addition to eliminating all problems, it also achieves a certain level of surface coloration that depends on appropriate fluidity, excellent level dyeing properties, and sharpness on the fabric, and at the same time improves desizing properties. Because of these properties, the sizing agent of the present invention can be used alone as a printing medium, and rice bran, particularly defatted rice bran, can be used effectively. Next, the present invention will be explained based on examples. Example 1 Using a predetermined amount of rice bran and defatted rice bran, and further using a predetermined amount of caustic soda, a predetermined amount of monochloroacetic acid or sodium monochloroacetic acid, carboxymethylation was performed using a hydrous organic solvent method, and then neutralization was performed using a conventional method. Summarize, purify, dry, and grind. At this time, if necessary, after the reaction, an aqueous solution may be prepared in which undissolved components are removed using a centrifuge. In this way, carboxymethylated (CM) rice bran and defatted rice bran having the analytical values shown in Table 1 were prepared.
Obtain a sample of Na salt.

[Table] The following base glue was prepared from the above sample and comparative sample. However, since rice bran and defatted rice bran are not water-soluble, they must be boiled at approximately 90°C for 2 hours.

[Table] Check the suitability for printing with disperse dyes for each base paste as follows. Sample fabric: Polyester twill Color Paste formulation: Kayalon Polyester Blue TS (Paste) (manufactured by Nippon Kayaku Co., Ltd.) 6.0% Citric acid 0.3% Original paste 60.0% Water 33.7% Total 100.0% Printing process: Flat screen printing → Pre-drying - High pressure steamer (HPS) → Flushing High temperature steamer (HTS) → Reduction cleaning → Flushing → Drying The test results are shown in Table 2.

【table】

[Table] The same applies to the following examples. From Table 2, rice bran and defatted rice bran have significantly improved suitability for textile printing if they are converted to a CM of 0.3 or higher. Also, as is clear from the PVI value, if
The PVI value also increases and fluidity suitable for mechanical printing is obtained. Example 2 The following base glue is prepared from the sample obtained in Example 1 and defatted rice bran.

[Table] Confirm the suitability for printing with reactive dyes for each base paste as follows. Sample fabric: Cotton Broad color Glue formulation: Remazol Turq.Blue G (manufactured by Hoechst) 60% Urea 10.0% HS powder (manufactured by Meisei Kagaku) 1.0% Soda ash 3.0% Original glue 60.0% Hot water 20.0% Total 100.0 % Printing process: Flat screen printing → Pre-drying →
High pressure steamer → flushing → soaping → flushing → drying The test results are shown in Table 3.

[Table] When using reactive dyes, it is practically impossible to use those that gel, so from Table 3, 0.7
It can be seen that it can be used if it is above. In addition, a PVI value of 0.7 or higher is suitable for mechanical printing.

Claims (1)

[Scope of Claims] 1. A printing paste characterized by containing as an essential component an alkali metal salt of carboxymethylated rice bran having an average degree of substitution in terms of purity of 0.3 or more. 2. The printing paste according to claim 1, which has an average degree of substitution in terms of purity of 0.7 or more when used in a reactive dye.