JPS63295778A - Production of dark dyed modified protein fiber - 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 (Industrial Field of Application) The present invention relates to a method for producing deep-dyed modified protein fibers.

(Conventional technology) Protein fibers such as domestic silkworms, millet silks, and wool are often used in high-quality textiles due to their excellent luster and texture, but their biggest drawback is that they cannot be dyed in deep, fast colors. This has created a bottleneck in creating high value-added products, such as diversifying design effects and producing fabrics with fibers of unique colors.

As a method for improving the deep dyeing of this type of protein fiber, a method has been proposed in which silk fiber is cationized by treatment with 3-chloro-2-hydroxypropyltrimethylammonium chloride (Japanese Patent Application Laid-open No. 225384/1984). .

In addition, some methods have been implemented in which the surface of dyed silk fibers is coated with a fluorine-based or silicon-based resin to change the reflectance of the aS surface, thereby making it appear darker.

(Problems to be Solved by the Invention) However, in the method of cationization using 3-chloro-2-hydroxypropyltrimethylammonium chloride, an excess of caustic alkali is applied to the ammonium chloride to form an epoxy ring, and This epoxy group is subjected to a chemical reaction on silk fibers at high temperatures using the above-mentioned caustic alkali as a catalyst.Therefore, since excessive caustic alkali is reacted at high temperatures, there is a problem in that the deterioration of silk fibers and the reduction in gloss become significant. There are some points.

On the other hand, in the method of coating the surface of silk fibers with fluorine-based or silicon-based resin, the processing operation is simple, but because of the surface coating, it is difficult to coat the surface of silk fibers. Even though the luster and texture of ata is damaged and the color appears to be somewhat dark, it is just an optical illusion and is not essentially dark dyeing.

(Means for Solving the Problems) The purpose of the present invention is to propose a method for modifying protein fibers that can solve the above-mentioned problems and also provide a higher dyeing effect than ever before. As a result of intensive research,
One or more of shrimp halohydrin and 2-methyl shrimp halohydrin is applied to the protein fiber in a water-organic solvent mixed solvent system, an organic solvent system, or a gas phase system to form halohydrin in the protein fiber. We propose a method for producing deep-dyed modified protein fibers, in which the groups introduced into the protein fibers are cationized by introducing groups into the protein fibers and then treating them with a tertiary amine or tertiary amine hydrochloride. It is something to do.

The protein fibers used in this invention include wild silkworms, millet silkworms,
Examples include silks such as Eri silkworms, wool, etc.

Furthermore, examples of helohydrins such as shrimp halohydrin and 2-methyl shrimp halohydrin used in this invention include chlorohydrin, bromohydrin, and the like.

Introduction of halohydrin groups into protein fibers is generally carried out using a neutral salt as a catalyst in an organic solvent system such as a lower alcohol such as isopropanol, a water-organic solvent mixture system, or a gas phase system. .

In this case, the neutral salts are NaCl, NaBr%Na
Sodium halide, K (:I, KBr, K1
Potassium halides such as LiC1, LiBr, Li1, etc., thiocyanates such as sodium salts, potassium salts, thiosulfates such as sodium salts, potassium salts, etc. can be used, among which thiocyanates Acid salts, thiosulfates are the most effective.

Specifically, protein fibers are impregnated with a neutral salt aqueous solution, and then heated in a bath of an organic solvent such as shrimp halohydrin or in a water-organic mixed solvent, or subjected to a gas phase treatment with shrimp halohydrin or the like under reduced pressure. However, a vat-batch method in which a neutral salt is added to a mixed bath of water and an organic solvent such as shrimp halohydrin, protein #a #1 is immersed, deliquified, and then left at room temperature is preferable. It is the most practically advantageous.

Next, the protein fibers are treated with a tertiary amine or tertiary amine hydrochloride to cationize the herohydrin groups introduced into the fibers.

In this case, it is most effective to use a lower alkyl amine such as trimethylamine or triethylamine as the tertiary amine, but since these tertiary amines exhibit high basicity in aqueous solution and damage protein fibers, hydrochloric acid It is preferable to use it as a salt.

As specific treatment conditions, for example, if trialkylamine hydrochloride is immersed in an aqueous solution containing 10 to 100 g/I and heated to room temperature to 50°C for about 30 to 120 minutes,
Sufficient cationization can be achieved.

(Effects of the Invention) In summary, according to the present invention, a helohydrin group is introduced into a protein fiber and the introduced halohydrin group is cationized as shown in the following formula. Cationization of the introduced halohydrin group can be carried out reliably under mild conditions.

Therefore, according to the present invention, it is possible to carry out color deepening modification without impairing the gloss, texture, etc. of protein fibers.

(Example) Examples of this invention will be shown below.

Example 1 A refined 12 momme silk habutae was immersed in the following treatment bath at room temperature for 3 minutes, and the liquid was drained into a 120 g pick-up.

Shrimp chlorohydrin 100g Isopropanol 300g Water 600g Potassium thiocyanate 80g Put this habutae in a polyethylene bag, seal it, and leave it at room temperature for 2
The sample was left to stand for 0 hours, then thoroughly washed with water, treated in an aqueous solution of 50 g/I triethylamine hydrochloride at 40°C for 40 minutes, washed with water, and dried.

The cationized sample and the unprocessed sample were mixed with dye 6z and acetic acid i.
, sx, and a bath ratio of 1:40.80"C,
Staining was carried out for 20 minutes. The results of this staining test are shown in Table 1.

As is clear from Table 1, it is clear that the cationized samples of the present invention exhibit remarkable deep dyeing properties for any anionic dye. Note that no decrease in color fastness or deterioration of m-fibers was observed.

Table 1 Example 2 Scoured and bleached silkworm silk yarn (35d) was immersed in the following treatment bath at room temperature for 5 minutes, and deliquified to 10 liters of pick-up 1.

2-methyl shrimp chlorohydrin 120g isopropanol 380g water
500g Sodium thiocyanate 100g This pestle silk thread was sealed in a polyethylene bag, left at room temperature for 24 hours, and then washed with water.

Next, 40'C in 60g/l trimethylamine aqueous solution
It was subjected to nR treatment for 50 minutes, washed with water, and dried.

This cationized pestle silk thread was dyed together with the unprocessed pestle silk thread in a Kayanol blue N2G3$ bath for 80"C1:10 minutes. As a result, the raw sample was only colored to the extent of contamination, whereas the cationized pestle silk thread was dyed. The sample was colored dark blue.

Claims (1)

[Claims] One or more of epihalohydrin and 2-methylepihalohydrin is applied to the protein fiber in a water-organic solvent mixed solvent system, an organic solvent system, or a gas phase system to introduce a halohydrin group into the protein fiber, and further A method for producing a highly dyed modified protein fiber, which comprises treating with a tertiary amine or tertiary amine hydrochloride to cationize the groups introduced into the protein fiber as described above.