JPS62272B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for printing natural fiber structures such as cellulose fibers, wool, and silk, or mixed structures containing these natural fibers, and particularly in a dry transfer printing method. It relates to a highly effective textile printing method.

Generally, natural fibers such as cellulose fibers, wool, and silk cannot be dyed with disperse dyes because they have no affinity for disperse dyes. In order to deal with these problems, materials that are not dyeable with disperse dyes are treated with disperse dye-dyeable resin and subjected to dry transfer printing. Special Publication in 1977 using special disperse dyes and swelling agents for mixed structures.
40593 and JP-A No. 50-12389, JP-A No. 50-38213, which utilize cross-linking agents and swelling agents in the dry transfer printing method.
The main methods include fiber processing methods such as those disclosed in Japanese Patent Application Laid-open No. 50-90788 and Japanese Patent Publication No. 50-29552, and cellulose fibers that do not have an affinity for disperse dyes are chemically treated with allylating agents, benzoylating agents, acetylating agents, etc. Japanese Patent Application Laid-open Nos. 18778-1877 and 99185-1977 are known to try to give affinity to disperse dyes by modifying them with chemicals, and many methods have been used for silk fibers. Special Publication No. 47-43156, which is treated with alcohol, is known. However, among these methods, although the method using the above-mentioned fiber treatment agent is possible using relatively simple equipment, it lacks clarity in color development and has poor color fastness, especially wet fastness. Not. On the other hand, conventionally known methods of chemically modifying cellulose require very expensive capital investment.

In order to solve these problems, the inventors first graft-polymerized a vinyl-based monomer to a cellulose fiber structure or a mixed structure containing cellulose fibers, which is inexpensive, has a clear color against disperse dyes, and An application was filed for an invention to obtain durable dyed cloth. As a result of further intensive research into these problems, the inventors have found that by using a monomer having the structure shown below, it is possible to improve natural fiber structures such as cellulose fibers, wool, and silk, or mixed structures containing these natural fibers. We discovered that it is possible to chemically modify disperse dyes to obtain durable dyed products with high affinity.

or That is, the present invention will be described in detail below. Using a monomer having the above structure, a chemical graft polymerization method is applied to a natural fiber structure such as cellulose fiber, wool, or silk, or a mixed structure containing these natural fibers. After modification, this is a method of direct or transfer printing using ink containing disperse dyes, oil-soluble dyes, basic dyes, benzine-soluble dyes, mordant dyes, vat dyes, etc. By carrying out this process, it is possible to extremely easily obtain a dyed product that has an extremely high affinity for the dyes, etc., is strong, and has a good texture.

Furthermore, the monomer having the above structure has relatively little odor characteristic of acrylic esters, has relatively little skin irritation, and is therefore easy to handle. In other words, the monomer having the above structure has less odor, toxicity, and irritation than methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, etc., which are generally known as graft polymerization modifiers for natural fibers. The acrylic esters or methacrylic esters with cyclic ether groups have higher activity than those with linear ether groups and are suitable for use in natural fibers. It is possible to perform grafting with an extremely simple operation. Therefore, it is possible to chemically modify natural fibers that have little affinity for disperse dyes into fibers that have extremely high affinity for disperse dyes using simpler and cheaper equipment, which is one of the major features of the present invention. Another major feature is that natural fiber structures graft-polymerized using monomers with the above structure experience extremely less hardening of the texture compared to when other monomers are used, and can be changed by selecting the conditions. It is possible to maintain the texture of the fiber structure before polymerization. It was also confirmed that when the present invention is applied to a dry transfer printing method using a transfer sheet appropriately printed with an ink containing a sublimable, vaporizable, or melt transferable heat transferable dye, the effect can be greatly enhanced. did. That is,
It has long been known that a drawback of the dry transfer printing method is that it tends to cause surface dyeing, but thread curling is more likely to occur during sewing, especially with relatively thin materials such as voile, jersey, and lawn, and this drawback is more noticeable. It was considered an easy material. Therefore, when graft polymerization is performed with a monomer having such a structure on a natural fiber structure such as cellulose fiber, wool, or silk that has such a structure, or a mixed structure containing these natural fibers, misalignment between each yarn occurs. It is less likely that this will occur, and the problem of thread return during sewing can also be solved. The natural fiber structure or mixed structure containing natural fibers described in the present invention may be various knitted fabrics, nonwoven fabrics, or even thread-like structures. Furthermore, in the present invention, two or more types of monomers, ie, a monomer having such a structure and another monomer for graft polymerization, may be used in combination. In the graft polymerization, the graft ratio is preferably in the range of 10 to 200% in order to maintain the characteristics of natural fibers and impart affinity to disperse dyes.

In addition, when graft polymerizing a monomer having such a structure to a cellulose fiber structure in the present invention, it is more effective to perform Malaprade oxidation using periodic acid before grafting the cellulose fibers. It has been found. That is,
By converting a portion of cellulose fibers into dialdehyde with periodic acid, grafting of monomers having such a structure becomes easier to occur, and at the same time, the dyeability of disperse dyes to graft-polymerized cellulose fibers is improved. It was confirmed that The Malaprade oxidation described here may be performed by a generally well-known method. As dyes that can be used in the present invention, all dyes that are generally commercially available as disperse dyes can be used, as well as disperse dyes described in Patent No. 440155, oil-soluble dyes, partially basic dyes, benzine-soluble dyes, and mordants. Dyes, vat dyes, etc. can be used. In order to make the present invention more clear, the present invention will be explained in detail using examples below.

[Example 1] (1) Graft polymerization was carried out with a tetrahydrofurfuryl acrylate monomer on cotton cloth according to the recipe shown below.

Cotton broadcloth...1g Tetrahydrofurfuryl acrylate monomer
...15c.c. Water ...300c.c. Ceric ammonium nitrate ...1g Processing temperature: 20°C, processing time: 15 minutes (2) Next, take out the cotton cloth, wash it thoroughly with benzene, and then When washed with water and allowed to dry, the cotton broadcloth increased in weight by approximately 25%.

(3) Next, this treated cloth is coated with a commercially available dry transfer printing paper made by Toppan Printing Co., Ltd. made of a disperse dye (as a dye, CI
Disperse Thread 60, CI Disperse Yellow 7, CI Disperse Blue 56), temperature 195℃, time 35 seconds, pressure 200
When transfer printing was carried out under the conditions of g/cm ² , a beautiful printed pattern with a good texture was obtained.

[Example 2] (1) The same cotton broadcloth used in Example 1 was immersed in a 0.05 mol sodium periodate aqueous solution at room temperature for 30 minutes (bath ratio 1:50) to perform Malaprade oxidation of cellulose. I went there.

(2) Next, after washing this treated cloth with water, (1) of Example 1 was applied.
Graft polymerization was carried out in exactly the same manner as shown in (2) above, and a cotton broadcloth with a weight increase of 25% was obtained in 8 minutes.

(3) Next, using the transfer printing paper used in (3) of Example 1, transfer printing was performed under the conditions of temperature 195°C, time 35 seconds, and pressure 200g/cm ² . A beautiful printed pattern that was clearer and had higher density than the obtained printed fabric was obtained.

[Example 3] (1) Using the recipe shown below, the cotton side was prepared in Example 2.
Graft polymerization was carried out using a tetrahydrofurfuryl methacrylate monomer onto a polyester/cotton blended plain woven fabric (65/35) which had been subjected to Malaprade oxidation as shown in (1) above.

Polyester/cotton = 65/35 (Malaprado oxidized cloth)...1.5g Tetrahydrofurfuryl methacrylate
……15c.c. Water ……300c.c. Ceric ammonium nitrate ……1.5g Treatment temperature: 35℃, treatment time: 20 minutes (2) Take out the treated cloth, wash thoroughly, and dry it. When the increase in weight was measured, an increase of 8% was observed.

(3) Next, apply Example 1 to this treated cloth in a usual manner.
When similar transfer printing was performed, a robust and beautiful printed pattern was obtained.

[Example 4] (1) Using the graft polymerization modified fabric obtained in Example 3 (2), screen printing was performed using a textile printing ink having the following formulation.

Carboxymethylcellulose 10 parts by weight Water 87 Resolin Red FBL (manufactured by Bayer)
3 Total: 100 parts by weight (2) This printed cloth was further steamed in high-pressure saturated steam at 130°C for 20 minutes, washed with water, and finished. A beautiful printed pattern was obtained.

[Example 5] (1) Graft polymerization was carried out with a tetrahydrofurfuryl acrylate monomer on a silk habutae fabric according to the recipe shown below.

Silk habutae 1g Tetrahydrofurfuryl acrylate monomer
15c.c. Water 300c.c. Ceric ammonium nitrate 1g Treatment temperature 20℃, treatment time 20 minutes (2) Next, take out this cloth, wash it thoroughly, dry it, and then dry it as in Example 1. When transfer printing was performed, a beautiful printed pattern with good texture and robustness was obtained.

[Example 6] (1) A 100% wool plain woven fabric was treated with the following recipe.

Ferrous ammonium sulfate 1.0g Sulfuric acid 1.0g Wool cloth 50.0g water 1 After being immersed for 2 hours at a treatment temperature of 25°C, it was air-dried.

(2) Next, grafting was performed on the treated wool fabric using the following recipe.

Tetrahydrofurfuryl acrylate 15c.c. 1N sulfuric acid 3c.c. (1) Treated wool 3g Water 100c.c. 0.03% hydrogen peroxide 15c.c. Treatment temperature 45℃, treatment time 40 minutes (3) Next After washing this treated fabric with benzene, washing with water and drying, dry transfer printing was performed in the same manner as in Example 1, and a beautiful printed pattern was printed on the wool fabric.

[Example 7] The cotton cloth obtained in Example 2 (1) was used as a sample. In a quartz glass container with a capacity of 100 c.c., 10 c.c. of tetrahydrofurfuryl acrylate monomer, 100 c.c. of distilled water, and 3 g of a sample were placed, stirred thoroughly, and sealed tightly. Next, this was irradiated for 2 minutes with a 1 KW high pressure mercury lamp from a distance of 100 mm. Thereafter, the sample was taken out, thoroughly washed with benzene, and then subjected to transfer printing in the same manner as in Example 1, resulting in a beautiful printed pattern.

Claims (1)

[Scope of Claims] 1. A natural fiber structure such as cellulose fiber, wool, silk, etc. or a mixed structure containing these natural fibers is subjected to graft polymerization with a monomer having the following structure, and then disperse dye or oil-soluble A dyeing method characterized by direct or transfer printing with ink containing a dye. or 2. The method according to claim 1, wherein the transfer printing is dry transfer printing using a heat transferable dye such as sublimation, vaporization, or melt transferability. 3. Claim 1, characterized in that the cellulose fiber structure or the mixed structure containing cellulose fibers is previously subjected to Malaprade oxidation treatment.
or the method described in paragraph 2.