JPS5831182A - Deep dyeing type size agent for printing - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to a printing paste having a good deep dyeing effect.

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.

Water-soluble when the size agent is used as a printing medium.

Heating stability, viscosity stability over time 9 Mechanical stirring stability.

Acid/alkali resistance, salt resistance, antibacterial properties, and reduction resistance.

There are a number of basic requirements to overcome, such as compatibility. The adhesive also has the following characteristics: reproducibility of the image after printing on the cloth, surface color development, level dyeing, and sharpness.

It plays an important role as a factor that affects various performances such as desizing properties.

Conventionally, sizing agents mainly include starch or its derivatives such as carboxymethyl starch (CMS), sodium alginate, and carboxymethyl cellulose (CMC).
) and natural gums such as galactomannan, which are used depending on the purpose of printing.

Among these, adhesives with excellent surface coloring properties are limited to CMS and CMC. In recent years, as resource conservation has been promoted, so-called deep dyeing pastes with increased color value are in demand in the textile printing industry in order to reduce the amount of expensive dyes used. However, sufficient surface color development cannot be obtained with CM Sli'L or CM CQt, so currently, surfactants called deep dyes and silica are used.

It is used in conjunction with extenders such as talc to reduce printing power.

These additives cause trouble because it is difficult to control them qualitatively or quantitatively depending on the type of fiber material or dye. On the other hand, although fresh konnyaku is used in a small portion of the hand printing field, it is not used as the main base material due to its ability to gel when mixed with alkali, cold water solubility, fluidity, and chemical resistance. Moreover, since it is not suitable for mechanical textile printing, its usage was small.

The present inventors conducted extensive research into a sizing agent that satisfies many basic conditions as a sizing agent for textile printing and has excellent surface coloring thorns.As a result, the inventors found that a konjac alkali metal salt of carboxymethylated konnyaku dyeing agent is capable of deep dyeing. It was discovered that it has excellent performance as a glue.

The printing paste according to the present invention has an average degree of substitution in terms of purity of 0.
．． 4 or more, and the viscosity of a 2% aqueous solution in terms of anhydride is 10 to 10,000 cps, and all essential components are alkali metal salts of carboxymethylated konjac.

Carboxymethylation of konjac is usually carried out by CMS or CM.
It is the same as the manufacturing method of C. In other words, konjac fine powder (or coarse powder) is treated with alkali (especially caustic soda),
Monochloroacetic acid or monochlorosodium acetate may be added to this to form an ether bond. If the polysaccharide is cellulose, the degree of etherification is 3.0, that is, all three hydroxyl groups per ton of anhydroglucose can be etherified, but generally the degree of etherification is 0.5 to 5. many.

Furthermore, the reaction method can be roughly divided into an aqueous medium method and a water-containing organic solvent method. The same is true for carboxymethylation of konjac, but since the alkaline aqueous solution has the property of gelling, it is better to use a water-containing organic solvent as the reaction method, but the process depends on the type and amount of the organic solvent. Care must be taken as the homogeneity of the reaction is different. The repeating structural unit of konjac consists of 1,6-bonds and 1,4-bonds with mannose:glucose=2=1, so its degree of etherification is expressed as the average substitution I9 per 6 carbon atoms. is called the average degree of substitution in terms of purity.

The average degree of substitution in carboxymethylation of konjac has a certain correlation with the flow behavior of its aqueous solution and its effect on the betting performance when it is applied as a printing paste. In the present invention, the average degree of substitution of the alkali metal salt in carboxymethylated konjac is required to be 0.4 or more. -Ii When the uniform degree of substitution is less than 0.4, water solubility and desizing properties as a sizing agent cannot be satisfied.

On the other hand, when used as a reactive dye, carboxymethylated konnyaku needs to have a degree of substitution of 1.0 or more. If the average degree of substitution is less than 1.0 or 7I:J+i, the color paste cannot be used in terms of gelation and desizing properties.The reason for this is that the reactive dye is This is because it chemically bonds to the hydroxyl groups of cellulose fibers and dyes them using reactive groups such as chlorinated triazine and vinyl sulfonic 4-acid, and naturally there is a possibility of bonding with printing pastes that have hydroxyl groups. , If the bond is misaligned, gelation of the colored paste or the phenomenon of adhesive peeling will occur.Such a phenomenon is caused by starch-based, natural energy-based, HEC, C
It is also observed to some extent in most adhesives such as MC (degree of substitution 0.5 to 07), which is a factor that prevents them from being put to practical use. This phenomenon is caused by the extreme substitution of primary hydroxyl groups in carboxymethylated konjac, which reduces the average degree of substitution to 1.
．． By setting the value to 0 or more, it will not be generated, that is, the binding with the reactive dye will be reduced, and it can be used as a sizing agent for textile printing.

The viscosity range of the 2% aqueous solution in the glue of the present invention is 10 to 1
0000cps, preferably 100-5000c
It is in the range of qs. In this case, a 2% aqueous solution is a value converted to an anhydride, and its viscosity is measured at 20 rpm and 25°C using a BH type precision d.The viscosity is 10 cp.
If it is less than s, 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 efficiency of the dye. contamination of the printing stand due to an increase in viscosity 1 (10 cps), which causes a decrease in the surface dyeing rate, and is also difficult to deal with from an economic point of view.On the other hand, if the viscosity exceeds 1
A secondary cause of the problem is a lack of 11 watts, which leads to a decrease in film strength.
: It is unsuitable because it tends to cause problems such as glue cracking, color splitting, and bleeding, and also causes problems such as fading due to insufficient printing IV.

The sizing agent of the present invention includes a direct dye, one acid, dye r1. Vat dyeing block 9 minutes 1lIi, dyeing block, naphthol dye, labidogen dye, vat dye, metal complex dye, (@ij''I, reactive dyeing old (average 1 ton conversion rate 1.0 or more''-)? 771:
It can be used as a printing medium when adjusting color paste. In addition, when preparing color pastes for various textile materials using these dyes, citric acid,
Organic acids used to adjust the pH of color paste such as tartaric acid, malic acid, and acetic acid, sodium chlorate, m-nitrobenzenesulfonic acid, ISf-based inhibitor, ammonium sulfate, ammonium tartrate, etc. In addition to salts and urea, dye dissolving agents, antifoaming agents, penetrants, slowing agents,
There is no problem in using various auxiliary agents suitable for printing processes such as level dyeing agents, deep dyeing agents, moisture absorbers, and humectants.

Although the printing paste according to the present invention exhibits sufficient basic physical properties and printing effects even when used alone as a printing medium, various thickening agents conventionally used such as starch, modified starch, natural gum, and sodium alginate can be used. , CMC, etc., so there is no problem in compatibility with them, so it is also possible to use them in combination to form a printing medium. The physical basis for the effectiveness of carboxymethylated konnyaku as a deep dyeing paste is thought to be that it has much better water-retaining properties than CMS or CMC, which were conventionally considered to be good.

In other words, although konnyaku itself has strong water-holding power,
This is probably because carboxymethylation imparts further hydrophilicity, and the dual effects of water absorption and water retention increase the water content during the coloring stage (especially in high-temperature steamers), helping the dye to migrate into the fiber.

When applying the size agent of the present invention as a printing medium, 7- Basic requirements such as water solubility, heating stability, and viscosity stability over time; 9. Mechanical stirring stability, acid/alkali resistance, chemical resistance, and antibacterial properties. In addition to eliminating the defects of various conventionally used sizing compositions in terms of properties, reduction resistance, and compatibility, it also maintains appropriate fluidity, level dyeing, and sharpness.
4: Improves desizing properties and at the same time provides unparalleled surface coloration (deep dyeing effect). Because of these properties, the size agent of the present invention can also be used exclusively as a printing medium.

Next, the present invention will be explained based on examples.

Example 1 Konjac flour is obtained by drying and drying Konjac root to coarse powder, and then removing cellulose and starch by wind-blowing. The refined konjac powder is carboxymethylated by a hydrous organic solvent method using a predetermined amount of caustic soda and a predetermined amount of monochloroacetic acid or sodium monochloroacetate, and then neutralized, purified, dried, and pulverized by a conventional method. As a result, samples having the analytical values shown in Table 1 were obtained.

B-Table 1 Note 1) DS: Average substitution modification per 6 carbon atoms 2) Viscosity is B H type viscosity liver RA1 and RA in 2% aqueous solution.
2 of 20 rpm.

Measure at 25°C.

(Left below) The following base glue is prepared from the obtained sample and known glue raw materials.

Original'mJA 1 F Commercialized Konnyaku Δ 7.2%
Aqueous solution A27 13 8.4% Boiled 3: // C8.6% A4:
E 1], 5% 〃A5:
F 17.7% 〃A6: //
H7, (1%〃A7:CMC(蔀1.2)
8.2%〃應8:Guar gum 1
4.0% 〃1/fa9: //
10.0% AIO: CM S (0.5)
1.0.5% 〃The suitability for printing with disperse dyes is confirmed for each base paste as follows.

Test fabric: Polyester fill citric acid 0.3% base paste
60.0% water 337% combination
Total: 100.0%→flow washing→reduction washing→flow washing→drying The results of printing suitability for disperse dyeing Fl are shown in Table 2.

(Margin below) 11- Part 2 The same applies to the following examples.

12- The results in the table are judged by observation and touch, and the evaluation is the superiority or inferiority of the samples used in the test.

a゛12 value standard: ◎Best, ○Good, △Fair, It can be seen that it also has excellent performance.

In addition, CM-formed konjac with DsO4 or higher has good other printing properties and also exhibits appropriate fluidity. 04 or less is level dyeing.

If it lacks sharpness, it cannot be used as a deep dyeing paste.

Example 2 In order to compare thick and thin fabrics, polyester decine was used as the sample fabric, and screen printing was performed at 1500
The suitability for printing with disperse dyes was confirmed in the same manner as in Example 1 except that a mesh was used. The test results are shown in Table 3.

(Left below) 14-3 From Table 3, I) S f), 40 and above 1- commercialization:
1 Nnyaku has excellent color value and deep dyeing properties.
Other properties are also good, and it also exhibits appropriate fluidity.

Example 3 The following base WJ is prepared from the sample obtained in Example 1 and a known adhesive base material 1.

Original paste Al: CMized Konnyaku C6, 5% aqueous solution 162:
tt D 7. (1% IjlG
, 3: E 8.8% 〃jIF
x4: G 15.5% 〃Ai,
5: CMC (DS 1.0) 6.7%
Bian 6: // (I almost 2J)) 8.4% 〃j67
: Sodium alginate 50% 〃For each base glue,
The printing suitability for reactive dyeing ζ1 is confirmed as follows.

Sample fabric: 100% cotton broad urea MS powder (manufactured by Kaisei Kagaku Co., Ltd.) 1.0% soda ash
3.0% Original glue 60.0% Total 100.0%Fll r3
Process: Flat screen printing (1000 meshes) →
Pre-drying → High-pressure steamer (HPS) → Flow condition → Soaping → Washing → Drying ・The results of printing suitability for reactive dyes are shown in Table 4 (margins below). 17- From Table 4, commercialized konjac It has been found that it has excellent color value and deep dyeing properties compared to the thickening agent often used for reactive dyes, and also exhibits appropriate fluidity. Also, DS
CM-formed konnyaku with a rating of 1.0 or higher can satisfy other properties, but those with a DS O87 tend to gel in the color paste, making it practically unusable.

Claims (2)

[Claims] (1) The average degree of substitution in terms of purity is 0.4 or more,
The viscosity of a 2% aqueous solution in terms of anhydride is 10 to 10 (1
00 cps of carboxymethylated konjac alkali metal salt as an essential ingredient! T! A thickening agent for thick dyeing type textile printing with r-like characteristics. (2) When used as a reactive dye, '44f a is characterized in that the average degree of substitution in terms of purity is 1.0 or more.
'l A printing paste according to claim 1.