JPS6024862B2 - Printing paste - Google Patents

Description

[Detailed description of the invention] The present invention relates to a paste for textile printing.

As a printing paste, a natural or semi-synthetic water-soluble polymer compound which is an amorphous solid, dissolves in water in a colloidal state, and has a high viscosity at a relatively low concentration is used, and is also called a base paste. It is.

A printing agent is a printing medium that is required to maintain shape in order to keep the design fixed on the fabric and faithfully reproduce the color image on the fabric. 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, basic considerations such as water solubility, heating stability, viscosity stability over time, mechanical stability, acid resistance, alkali resistance, salt resistance, antibacterial properties, reduction resistance, and compatibility are important. There are many necessary conditions.

Furthermore, the sizing agent 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 color development, level dyeing property, sharpness, and desizing property. Conventionally, sizing agents have mainly included starch or its derivatives, sodium alginate, cellulose derivatives represented by carboxymethyl cellulose, and natural gums such as galactomannan, and these have been used depending on the purpose of the printing process. There is.

However, at present, starch or its derivatives are characterized by surface coloring properties during printing, but they have defects in machine stability, acid resistance, reduction resistance, uniformity, sharpness, desizing properties, etc. There is. Sodium alginate has excellent performance in beam uniformity and desizing properties, but it also has poor heating stability, acid resistance,
Problems arise due to defects in alkali resistance and surface color development. Carboxymethylcellulose, which is frequently used among cellulose derivatives, satisfies various properties such as surface coloration, desizing properties, heat stability, and antibacterial properties, but it also has poor acid/alkali resistance, chemical resistance, and mechanical damage resistance. There are defects in stability, beam uniformity, etc. Natural gums such as galactomannan satisfy most of the properties such as mechanical stability, acid resistance, and chemical resistance, but they have deficiencies in reduction resistance, antibacterial properties, and surface coloring properties, and they are also difficult to use in high-temperature steamers. Poor desizing properties in high-temperature coloring such as Samosol are a fatal flaw. In this way, the glue
Since they each have their own characteristics and drawbacks depending on their composition and chemical structure, they generally cannot satisfy all required performances. Therefore, each size agent is often used in combination depending on the printing method, fiber material, coloring material, etc. The present inventors have conducted extensive research into a sizing agent that satisfies many basic conditions as a sizing agent for textile printing by compensating for the drawbacks of conventional sizing agents, and has excellent printing performance. It was discovered that alkali metal salts of glycans have unexpectedly excellent performance as printing pastes. The printing paste according to the present invention has an average degree of substitution in terms of purity of 0.9 to
2.6, and the viscosity of a 2% aqueous solution in terms of anhydride is 5 to 500 ps as an essential component. The heteroglycan used in the present invention is a complex polysaccharide, such as locust Bingham, guar gum, siratu gum, tamarind gum, and gum arabic.

In this case, the molecular chain length of the heteroglycan is important because it greatly influences various performances of the carboxymethyl heteroglycan. Carboxymethylation of heteroglycans is generally the same as the method for producing carboxymethyl cellulose or carboxymethyl starch.

That is, heteroglycan, which is a complex polysaccharide, is treated with an alkali (especially caustic soda), and monochloroacetic acid or monochloroacetic acid sodium is added thereto to form an ether bond. If the polysaccharide is cellulose, the degree of etherification is 3.
0, that is, all three hydroxy acids per unit of anhydroglucose can be etherified, but the degree of etherification is generally 0.5.
It is often ~1.5. Although this is the same for carboxymethylation of heteroglycans, the repeating structural units for each raw material are complex, so the degree of etherification is expressed as the average degree of substitution per 6 carbon atoms.
This is called the average degree of substitution in terms of purity. The average degree of substitution in carboxymethylation of heteroglycans has a certain correlation with the flow behavior of its aqueous solution and its effect on various performances when it is applied as a printing paste.

For example, in the case of thickeners for reactive dyeing, while carboxymethyl cellulose requires an average degree of substitution of 1.2 or more (extremely substituted primary hydroxyl groups), carboxymethyl heteroglycan Therefore, it becomes possible to use even a lower average degree of substitution than that. In the present invention, the average degree of substitution of the alkali metal salt of carboxymethyl heteroglycan is required to be in the range of 0.9 to 2.6. Even if the average degree of substitution is less than 0.9, it satisfies the above-mentioned basic printing conditions and most of the printing suitability. It is inferior to methylcellulose. On the other hand, because the repeating structural units of heteroglycans are complex, the maximum average degree of substitution is not constant; for example, in tamarind gum, the maximum average degree of substitution is 2.5 to 2.6. The molecular chain length of heteroglycans, which greatly affects the performance of carboxymethyl heteroglycans, is generally expressed by the average degree of polymerization, which is usually used as a substitute characteristic value by measuring viscosity. Conversely, those with a low average degree of polymerization exhibit low viscosity. 2 in the adhesive of the present invention
% aqueous solution is in the range of 5 to 500 specific ps, preferably in the range of 100 to 500 specific ps. In this case, 2
% aqueous solution is a value converted to anhydride, and its viscosity is measured using a BH type viscometer at 2pm, 2yo.

If the viscosity is less than &ps, the viscosity is too low and the paste solid content required to obtain the appropriate viscosity for the color paste becomes excessive, which reduces the effective utilization rate of the dye and at the same time causes an increase in the amount of backflow. This causes contamination of the printing table and a decrease in the surface dyeing rate, and is also economically unfeasible. - On the other hand, if the viscosity exceeds 500 ps, there will be a shortage of solid glue in the colored paste, which will cause adhesive cracking, color migration, and bleeding phenomena due to a decrease in film strength, as well as fading due to insufficient printing amount. It is inappropriate because it tends to cause problems such as The lake agent of the present invention can be applied as a printing medium when preparing color pastes consisting of direct dyes, acid dyes, architectural dyes, disperse dyes, naphthol dyes, rapidogen dyes, vat dyes, metal tin salt dyes, and reactive dyes. It is. In addition, when adjusting color pastes for 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 nitrobenzene sulfonate, salts such as ammonium sulfate and ammonium tartrate, and urea, dye dissolvers, sterilizing agents, penetrants, twill dyes, and uniform beams. There is no problem in using various auxiliary agents suitable for the printing process, such as drying agents, absorptive agents, moisture absorbing agents, and heat insulating agents. 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 pastes such as starch, natural gum, sodium alginate, or various substitutes. Since there is no problem with the compatibility with carboxymethylcellulose, it is also possible to use them together as a printing medium.

When applying the size agent of the present invention as a printing medium, the basic requirements are water-removal properties, heat stability, viscosity stability over time,
It eliminates the deficiencies of various conventionally used lake agent compositions in terms of mechanical stability, acid/alkali resistance, chemical resistance, antibacterial properties, reduction resistance, compatibility, etc., and also provides adequate flowability. It expresses on the cloth a certain surface coloration that depends on the nature, excellent beam uniformity, and sharpness, and at the same time, it significantly improves the desizing property, which is the biggest defect of natural gum.

Because of these properties, the size agent of the present invention can be used alone as a printing medium. Next, the present invention will be explained based on examples.

Example 1 Using a predetermined amount of tamarind gum and guar gum as heteroglycans, and using a predetermined amount of caustic soda, a predetermined amount of monochloroacetic acid or sodium monochloroacetate, carboxymethylation was performed by a conventional method, and then neutralization, Perform purification, drying, and grinding.

As a result, a sample of carboxymethyl heteroglycan having the analytical values shown in Table 1 is obtained. Table 1 Note 1) DS: Average degree of substitution per 6 carbon atoms Note 2) Viscosity is measured using a BH type viscometer R No. in a 2% aqueous solution. 1 and no. Measured at 2.2 Pm, 25°C.

The next base glue is adjusted by appropriately selecting from the obtained samples.

Original rudder. 1: CMized tamarind gum A 15% aqueous solution M
．． 2: CM modified marine Indian gum B I 9% aqueous solution No. 3
:CMized tamarind gum C 30% aqueous solution M. 4:CM
Guar gum A 6% aqueous solution No. 5: CMized guar gum B 8% aqueous solution Tsumugi. 6: 13% aqueous solution of CMized guar gum C The suitability of each base paste for dispersion dyes was confirmed as follows.

Offering cloth: Polyester twill Colored paste prescription: Kayalon PolyesterB1ue
Printing process: Flat screen printing (1200 mesh) → Pre-drying - <High-pressure steamer HTS) > - Washing - High-pressure steamer HTS) → Reduction cleaning → Run-washing - Drying The results of printing suitability for disperse dyes are It is shown in Table 2.

Table 2 Note 1) Color value (K/S) is lateral color difference meter ZIOO
The color value is measured using an IDP model (manufactured by Nippon Denshoku Kogyo Co., Ltd.), and the larger the value, the greater the color value.

Note 2) Evenness, sharpness, shelving property, permeability, etc. are determined by observation and touch. Evaluation criteria: ◎Best, 〇Good, △Average,
From the same table 2, DS is 1 for the examples below × defective.
．． It has been found that when it is 0 or more, the performance is improved overall, and the fluidity is also good.

Example 2 The suitability of ink lacquer for disperse dyes was confirmed in the same manner as in Example 1, except that polyester decine was used as the cloth to compare thick and thin fabrics, and a screen-like scale was used with 1500 mesh. do. The test results are shown in Table 3. Table 3 From Table 3, it can be seen that when the DS is 1.0 or more, the performance is good and the fluidity is also good.

Example 3 The following base glue was prepared by appropriately selecting from the samples obtained in Example 1.

Original seaboard. 1: CMized tamarind gum A II% aqueous solution M
．． 2: CM tamarind gum D II% aqueous solution. 3:
CMized tamarind gum E 16% aqueous solution M. 4: CMized tamarind gum F 28% aqueous solution No. 5: CMized guar gum A 5% aqueous solution axis. 6: Commercialized guar gum ○
8% aqueous solution shame. 7: Commercialized guar gum B
The compatibility of each 15% aqueous solution base glue with ink lacquer against reactive dyes was confirmed in the following manner.

Test fabric: Line broad color glue prescription: Remazo ITurq. Vice ue G (manufactured by Hoechst) 6.0% urea
10.0% MS powder (manufactured by Meisei Chemical Co., Ltd.)
1.0% soda ash 3.0% Printing process: Sefrat screen printing lacquer (1000 mesh) → Pre-drying → High-pressure steamer (HPS) → Rinse → Soaping → Rinse → Check suitability for printing against dry reactive dyes The results are shown in Table 4.

Table 4 From Table 4, DSO. 9 or more are reactive dyes
Ru.

Claims (1)

[Claims] 1. The average degree of substitution in terms of purity is 0.9 to 2.6,
The viscosity of a 2% aqueous solution is 5 to 5000 cp in terms of anhydride.
A thickening agent for printing, characterized in that it contains an alkali metal salt of carboxymethyl heteroglycan, which is s, as an essential component. 2 Heteroglycans include locust bingham, guar gum,
2. The printing paste according to claim 1, which is gum shiratsu, tamarind gum, or gum arabic.