JPS6215675B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a transfer printing method for cellulose fibers or structures containing the same.

In the past, attempts have been made to dye cellulose fibers well using dyes such as disperse dyes that do not originally have the ability to dye cellulose fibers, and attempts have been made to uniformly dye blended fabrics of cellulose fibers and synthetic fibers. Many things have been done. These attempts have increased in number with the development of sublimation transfer printing methods that mainly use disperse dyes. , after treatment with disperse dye-dyeable resin, etc.
Disperse dyes include methods of transfer printing, methods of chemically modifying cellulose fibers using agents such as benzoylating agents and acetylating agents, and methods of modifying cellulose fibers using benzylating agents such as benzyl chloride. Many attempts have been made to create compatibility with However, among these methods, the methods using swelling agents, dyeable resins, and crosslinking agents are possible using relatively simple equipment, but they lack clarity in color development and are difficult to dye. Poor fastness, especially wet fastness. On the other hand, conventionally known methods of chemically modifying cellulose have poor workability due to the irritation and odor of the chemicals themselves.
Moreover, it requires very expensive equipment investment.

For example, there is a method of chemical modification using an acetylating agent or benzoylating agent and then transfer printing.
Acetylating agents, benzoylating agents, etc. have a pungent odor and are easily hydrolyzed if stored in the air for a long time. I stopped talking. Furthermore, those chemically modified using an acetylating agent also have the disadvantage of poor washing fastness.

In order to solve these problems, the inventors chemically modified cellulose fibers or mixed structures containing cellulose fibers to make them dyeable with disperse dyes by using an acid chloride such as P-toluenesulfonyl chloride in advance. dye, then disperse dye, oil-soluble dye,
This is a printing method using mordant dyes, basic dyes, etc.

Chemical modification using an acid chloride such as P-toluenesulfonyl chloride of the present invention is easy to handle because the odor of the reagent and hydrolysis in the air are small compared to acetylating agents and benzoylating agents. can be,
The reforming method also does not require expensive equipment and can enable chemical reforming with relatively simple equipment. Chemical modification using P-toluenesulfonyl chloride has been reported in various literatures, but these methods require long modification times and are difficult to produce, considering the waste of reagents. It was unsuitable for sex and impractical.

Therefore, the present invention uses an acid chloride such as P-toluenesulfonyl chloride with a relatively simple device,
Chemical modification methods including practical aspects and productivity were investigated. As a result, a method of obtaining a modified fabric by applying an acid chloride such as P-toluenesulfonyl chloride in advance and then dipping it in an aqueous solution containing an alkaline agent such as sodium hydroxide, and a method of obtaining a modified fabric by applying an acid chloride such as P-toluenesulfonyl chloride, It has been found that a method of obtaining a modified fabric by applying an alkaline agent to the fabric and then baking it is a good process from both a practical and production standpoint. This is a process that has unprecedented productivity and allows for continuous processing.

The invention will now be described in detail.

As a modification process, there is a method described in the literature, in which the alkali cellulose is made and then reacted in a P-toluenesulfonyl chloride solution.

In these processes, the reaction progresses well and modification is performed at the beginning, but the modification gradually stops. This is because the alkaline agent and water get mixed into the P-toluenesulfonyl chloride solution, and even P-toluenesulfonyl chloride, which does not participate in the reaction, is hydrolyzed, leading to wasted reagents and was found to be impractical. . Therefore, we first considered a method of applying an acid chloride such as P-toluenesulfonyl chloride and then treating it with an alkali agent. We tried a method of applying the agent and then causing a reaction by baking. The former method, that is, the method of reacting in an alkaline aqueous solution, is a sufficient improvement, but as mentioned above, there is a concern that it may lead to wastage of the alkaline agent. Therefore, we added an acid chloride such as P-toluenesulfonyl chloride,
After that, after applying an alkali agent, various reactions by baking were attempted, and the results were as follows:
It has been found that a sufficiently modified fabric can be obtained under conditions of seconds to 20 minutes. This method does not waste acid chlorides such as P-toluenesulfonyl chloride and alkaline agents, is practical, can be continuous, and has good productivity. Furthermore, if you use a treated cloth that has been swollen with an alkali such as sodium hydroxide, then washed with water, and replaced with a water-compatible solvent such as acetone, ethyl acetate, methyl ethyl ketone, methanol, ethanol, etc., the property will be further improved. It was also found that this was promoted.

Dry transfer of the thus obtained modified fabric using, for example, a commercially available transfer paper using a sublimable disperse dye, resulted in good dyeability to the disperse dye, resulting in a print with high density and good color fastness. I was able to get things.

Acid chlorides that can be used in this method are compounds having the structure shown below.

This method can also be used in combination with other conventional methods. For example, the modified fabric obtained by the above method may be dyed with a resin that is dyeable with disperse dyes, such as
Amino alkyd resin, polyamide, urethane,
When treated with vinyl chloride, vinyl acetate, polyester, acrylic, acetal, polyvinyl alcohol, vinylidene chloride, vinyl acetal, styrene, polycarbonate, epoxy resin, etc., and then dry transfer printing, the density, hue color, and depth can be improved. etc. can be further improved. In addition, modified fabrics include dimethylol urea, dimethylol propylene urea, dimethylol hydroxyethylene urea, dimethylol uron, trimethylol melamine, trimethoxymethyl melamine, hexamethoxy methyl melamine, dimethylol methyl triazone, dimethylol ethyl triazone, Dimethylol hydroxyethyl triazone, dimethylol methyl carbamate, dimethylol ethyl carbamate, dimethylol hydroxyethyl carbamate, N-methylol acrylamide, methylol glyoxal monourea, methylol glyoxal diurea, formaldehyde, tetraoxane, glitaraldehyde, diepoxide, divinyl sulfone , 4-methoxy-5-dimethyldimethylolpropyleneurea, a fiber crosslinking agent such as tetramethylolacetylene diurea, and a crosslinking catalyst, such as an organic acid such as acetic acid or maleic acid, an ammonium salt such as ammonium chloride, ammonium sulfate, or ammonium hydrogen phosphate, Treated with amines such as ethanolamine hydrochloride, 2-amino-2-methylpropanol hydrochloride, magnesium chloride, zinc nitrate, zinc chloride, magnesium nitrate, zinc borofluoride, aluminum chloride, magnesium phosphate, etc., and cross-linked at the same time as dry transfer printing. By crosslinking the agent, it is possible to improve the hand, and for example, it is possible to freely adjust the finish to hard or soft, and it also leads to an increase in density, which further enhances the effect. Furthermore, a polyhydric alcohol such as ethylene glycol can be used in combination, for example, a method in which fibers are pretreated with a polyhydric alcohol, then treated with the above acid chloride, and then treated with an alkali for modification, or in an acid chloride bath. Possible methods include mixing polyhydric alcohol. Polyhydric alcohols include propylene glycol monoacetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, trimethylene glycol, 1.3-butanediol, 2.3-butanediol, and 1.4-butane. Diol, 1.5-pentanediol, 3.4-hexylene glycol, octylene glycol, glycerin,
Glyceryl diacetate, glyceryl triacetate, glyceryl monobutyrate, glycerin
α-monomethyl ether, glycerin-α, γ-
These include dimethyl ether, glycerin-α-monoisoamyl ether, glycerin-α, γ-dichlorohydrin, trimethylolpropane, and the like.

The cellulosic fibers applicable to this method include natural cellulose fibers such as cotton, regenerated cellulose fibers such as viscose rayon, and mixtures of these fibers and synthetic fibers such as polyester are also applicable. be able to.

Furthermore, as the acid chloride applied to this method, P-toluenesulfonyl chloride and the like can be used.

Further, as the alkaline agent used in this method, sodium hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, etc. can be used.

Furthermore, the dyes that can be used in the present invention include disperse dyes, oil-soluble dyes, mordant dyes, basic dyes, vat dyes, etc., which may or may not have sublimation properties, and can be printed by direct printing or transfer printing.
In particular, when a sublimable dye is used, a dry transfer printing method is possible.

This will be explained below using examples.

Example 1 (1) A mercerized polyester/cotton (65/35) broadcloth was previously immersed in a 2% aqueous sodium hydroxide solution for 2 minutes, washed with water, and immersed as it was in an acetone solution. P-toluenesulfonyl chloride was added to the soaked cloth in acetone.
Immerse it in a 30% dissolved solution and squeeze it to a rate of 80
% and dried at 70°C.

The treated cloth was immersed in a 2% aqueous sodium hydroxide solution, squeezed at a squeezing rate of 80%, and then baked in an oven at 140°C for 3 minutes. Thereafter, it was washed with water and dried to obtain a modified product.

(2) Next, a transfer paper was obtained by gravure printing on a 60 g/m ² single-sided starch-coated paper using an ink having the composition shown below.

<Ink> {Sumikalon Red E-FBL (base powder) {manufactured by Sumitomo Chemical Co., Ltd.} 10 parts Ethyl cellulose N-7 9〃 Surfactant 1〃 Isopropyl alcohol 40〃 Ethanol 40〃 } (3) (1) Modification When the transfer paper (2) was superimposed on the cloth and heat and pressure was applied for 40 seconds at a temperature of 200°C and a pressure of 300g/cm ² to perform transfer printing, the polyester and cotton parts had the same red density. I was able to obtain printed fabric. In addition, when measured using the washing fastness (A-2) method based on JIS, it was grade 5,
It was a sturdy printed cloth.

Example 2 (1) A modified fabric was obtained as in Example-1. Next, the modified fabric was immersed in a solution of the following formulation (a), then squeezed to a squeezing rate of 80%, pre-dried at 100°C for 2 minutes, and then baked at 150°C for 3 minutes.

(B) Prescription {Sumitex Resin AMH3000 (Sumitomo Chemical) 10 parts by weight (acrylic acid ester emulsion) Sumitex Accelerator X-80 (Sumitomo Chemical) 1 〃 Water 90〃 } (2) Next, transfer The paper was prepared as in (Example 1).

(3) Overlap the modified cloth (1) with the transfer paper (2),
When the transfer was performed by heating and applying pressure at a temperature of 200℃, a pressure of 300g/cm ² , and a time of 40 seconds, it was possible to obtain a printed fabric with the same red density, color, and depth for the polyester and cotton parts. Ta. When the washing fastness was measured, it was grade 5 according to method (A-2), indicating that the printed fabric was fast. In addition, when we measured the color density of transfer printed fabrics with and without resin treatment using a Macbeth reflection densitometer, the former was 1.03;
The latter was 1.28, indicating a clear increase in concentration.

Example 3 (1) A mercerized polyester/cotton (65/35) knit cloth was pre-soaked in a 20% aqueous sodium hydroxide solution for 2 minutes, washed with water, and then immersed in an acetone solution. P the soaked cloth
- Immerse in toluenesulfonyl chloride 30% acetone solution, squeeze to 100% squeezing rate, then 60%
It was immersed in a 20% sodium hydroxide aqueous solution kept at ℃ for 45 minutes, then washed with water and dried.

(2) Next, dry transfer printing paper made of disperse dye was used on this modified cloth at a temperature of 200℃, a pressure of 300g/cm ² , and a time of
When transfer printing was performed for 40 seconds, a beautiful printed pattern was obtained.

Example 4 (1) A mercerized polyester/cotton (65/35) broad cloth was immersed in a 30% triethylene glycol aqueous solution for 2 minutes, and the squeezing rate was 80%.
I narrowed it down to The cloth was immersed in a 30% P-toluenesulfonyl chloride solution in acetone, then squeezed to a squeezing rate of 80%, and then dried at 70°C for 1 minute.

The treated cloth was immersed in a 2% aqueous sodium hydroxide solution, squeezed to a squeezing rate of 80%, and then baked in an oven at 140°C for 5 minutes. Then, it was washed with water and dried.

(2) Next, transfer printing was performed on this modified fabric using a dry transfer printing paper made of disperse dye at a temperature of 200℃, a pressure of 300g/cm ² , and a time of 40 seconds. A beautiful printed pattern was obtained. In addition, when the color density of the printed fabric treated with triethylene glycol and the printed fabric that was not treated was measured using a Macbeth reflection densitometer, the former was
1.32, and the latter was 0.95, indicating a clear increase in concentration.

Example 5 (1) A modified fabric was prepared as in (Example 1). Next, the modified fabric was immersed in a solution with the following formulation (b), then squeezed to a squeezing rate of 80%, pre-dried at 100°C for 2 minutes, and then baked at 150°C for 3 minutes.

(b) Prescription {Sumitex Resin NS-16 (Sumitomo Chemical)
10 parts by weight Sumitekus Accelerator X-80
(〃) 1 〃 SUMITEX SOFTNER L
(〃) 1 〃 Water 90 〃 } (2) Transfer paper was prepared as in Example 1.

(3) Overlap the modified cloth (1) with the transfer paper (2),
When the transfer was performed by heating and applying pressure at a temperature of 200° C., a pressure of 300 g/cm ² , and a time of 40 seconds, a printed fabric with the same red color density in the polyester and cotton portions and a good texture was obtained. When the color density of the transferred printed fabrics treated with a crosslinking agent and those not treated with a crosslinking agent was measured using a Macbeth reflection densitometer, the former was 1.20 and the latter was 1.08, indicating an increase in density.

Claims (1)

[Claims] 1 A cellulose fiber structure and a mixed structure of cellulose fibers and synthetic fibers are chemically modified by adding an acid chloride having the following structure, then adding an alkali agent, and further heat-treating the structure. and then directly or transfer printing with a disperse dye, a mordant dye, a basic dye, a vat dye, etc. 2. The method according to item 1 above, wherein the transfer printing is dry transfer printing using a heat transferable dye such as sublimation, vaporizability, or melt migration dye.