JPH07292571A - Fiber structure made of silk fiber having whitening resistance and method for producing the same - Google Patents

Abstract

(57) [Summary] [Object] To provide a fiber structure composed of silk fibers having whitening resistance in which darkening is not noticeable and a method for producing the same. [Constitution] 5% by weight sodium hydroxide aqueous solution at 65 ° C. for 6 hours
It is composed of silk fibers crosslinked with an epoxy compound having a solubility of 30% by weight or less when immersed for 0 minutes, and has an L value of 2
It is characterized by being dyed to 0 or less. In addition, the production method is such that a fiber structure made of silk fibers dyed with an L value of 20 or less is prepared by adding a water-soluble polyfunctional epoxy compound,
Using an aqueous solution containing one kind of catalyst selected from sodium sulfate or sodium chloride, dip treatment is performed at a temperature of 90 ° C. or lower, or the above aqueous solution is applied to the solution at room temperature of 30 ° C. or lower in a state of preventing evaporation of water. Characterized by placing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber structure made of silk fiber having whitening resistance and a method for producing the same.

[0002]

2. Description of the Related Art A fiber structure composed of silk fibers is known, and is dyed in a dark color such as black or navy blue, and is provided as socks or the like by taking advantage of the comfort of silk fibers.

[0003]

However, socks made of silk fibers dyed in dark colors are not whitened after only a few hours of coloring due to the synergistic effect of moisture in the shoes and friction with the shoes when walking. It has the drawback that it does not expose the foot to the public. This is because the silk fibers are fibrillated by friction under wet conditions and are not noticeable in white or light colors, but are noticeable in dark colors.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a fiber structure made of silk fibers having whitening resistance in which whitening is not noticeable even in a dark color and a method for producing the same. To do.

[0005]

The present invention comprises a silk fiber crosslinked with an epoxy compound having a solubility of 30% by weight or less when immersed in a 5% by weight aqueous sodium hydroxide solution at 65 ° C. for 60 minutes. A fiber structure made of silk fiber having a whitening resistance, which is characterized by being dyed with a value of 20 or less.

The present invention will be described below.

The silk fiber of the present invention includes domestic silk thread and wild silk thread. Examples of the fiber structure include raw silk, silk spinning, knitting, woven fabric and non-woven fabric using them. For example, as silk spun yarn for socks, 5, 10, 30 single yarn,
60, 80, and 100 count twin yarns are preferably used.

In the present invention, the solubility means the weight reduction of silk fiber after the silk fiber is immersed in a 5 wt% sodium hydroxide aqueous solution at 65 ° C. for 60 minutes. Solubility is 30% by weight or less,
It should preferably be 25% by weight or less. Solubility is related to whitening, and if the solubility is 30% by weight or less, almost no whitening occurs when worn.

[0009] In the present invention, L value measured refers to the L ^* a ^* b ^* color system of L ^* using a spectrophotometer and a lower the dark. A fiber structure made of conventional silk fiber,
There is no dye that has an L value of 20 or less and does not whiten when worn.

Such a fiber structure comprises a fiber structure composed of silk fibers dyed with an L value of 20 or less, a water-soluble polyfunctional epoxy compound, and a catalyst selected from sodium sulfate or sodium chloride. Using an aqueous solution, 90
A fibrous structure composed of silk fibers having whitening resistance, which is characterized by being immersed at a temperature of ℃ or less, or by being placed in a room temperature of 30 ℃ or less in a state where the above aqueous solution is applied to prevent evaporation of water. And a method for producing the same, or a fiber structure made of silk fibers, wherein the pH of the aqueous solution containing the water-soluble polyfunctional epoxy compound and the catalyst is less than 11, and the pH of the aqueous solution containing the water-soluble polyfunctional epoxy compound and the catalyst is A fiber structure made of silk fibers having whitening resistance, which is characterized by imparting a catalyst of 9 or more, and then dyeing it with an acid dye or a metal-containing dye, and having an L value of 20 or less, and a method for producing the same. Can be manufactured by.

The water-soluble polyfunctional epoxy compound used for crosslinking the silk fiber of the present invention is diglycidyl ether or polyglycidyl ether having an epoxy equivalent of 5
00 or less, for example, ethylene glycol, polyethylene glycol, propylene glycol,
Polypropylene glycol, glycerin, sorbitol, polyglycerol, pentaerythritol, tris (2-hydroxyethyl) isocyanurate, trimethylolpropane, neopentyl glycol, 1,4 butanediol, phenol ethylene oxide, diglycidyl ether of lauryl alcohol ethylene oxide or Examples include polyglycidyl ether.

Although the amount of the water-soluble polyfunctional epoxy compound applied varies depending on the epoxy equivalent, etc., it is 1 to 20% by weight with respect to the silk fiber by the dipping method, and it is 3 with the water evaporation prevented.
The so-called cold batch method, which is kept at room temperature below 0 ° C., has a content of 3 to 50% by weight based on the silk fiber, and the pad-dry-steam, pad-dry-cure, and pad-dry-cold batch methods have a content of 3 to 50% by weight. is there.

When a fiber structure made of dyed silk fiber is subjected to an epoxy crosslinking treatment, sodium sulphate or sodium chloride is used as a catalyst in order to prevent the dye from oozing out. When the epoxy crosslinking treatment precedes the dyeing, the pH of the aqueous solution containing only the catalyst is less than 11 and the pH of the aqueous solution containing the water-soluble polyfunctional epoxy compound and the catalyst is 9 or more so that the crosslinking can be efficiently performed. Is used. Specific examples include monocarboxylic acid, dicarboxylic acid, tricarboxylic acid, aminocarboxylic acid, sulfuric acid, hydrochloric acid,
Examples thereof include alkali metal salts and alkaline earth metal salts of nitric acid, thiocyanic acid and thiosulfate. The amount of the catalyst used is generally 0.5 to 20% by weight of the total amount of the processing liquid, preferably 1 to
It is 15% by weight.

When the fiber structure made of dyed silk fiber is subjected to the epoxy crosslinking treatment, the crosslinking treatment condition is 90 ° C. or less, preferably 90 ° C. or less, in an aqueous solution of the above-mentioned combination of the water-soluble polyfunctional epoxy compound and the catalyst. Is immersed at a temperature of 60 to 90 ° C. for 30 to 180 minutes, or 30 ° C. or less in a state in which the aqueous liquid is applied to prevent evaporation of water,
It is preferably placed at room temperature of 10 to 30 ° C. The time to leave at room temperature depends on the room temperature and the composition of the processing solution,
It is preferable to allow the reaction to proceed sufficiently over a time period.
If the reaction is allowed to proceed sufficiently within 20 hours, the treatment liquid may become unstable and the fibers may be cured. When left for a long period of time, it is desirable to wind the film on a roll and rotate it so that adhesion unevenness does not occur. After the crosslinking treatment, washing with hot water and washing with water are performed. As the dipping treatment device, a yarn dyeing machine or an over-meyer can be applied to the yarn, and a paddle dyeing machine can be applied to the sock, but the processing with the yarn is preferable from the viewpoint of difficulty in rubbing and feeling.

When the epoxy crosslinking treatment precedes the dyeing, the crosslinking treatment conditions include dipping treatment, pad-dry-steam, pad-dry-cure, pad-dry-
Processing methods such as cold batch and pad-cold batch can be performed. In the dipping treatment method, for example, the treatment is performed at a temperature of 50 to 110 ° C., preferably 60 to 95 ° C. for 30 to 180 minutes.
In the pad-dry-steam method, for example, after applying an aqueous solution, it is dried at a temperature of 50 to 100 ° C. and then 150 ° C.
Steaming with the following heating steam or steaming with saturated steam at 120 ° C. or lower, preferably less than 110 ° C. is performed. In the pad-dry-cure method, for example, after applying an aqueous solution, it is dried at a temperature of 50 to 100 ° C. and then 120 to 1
Cure at a temperature of 70 ° C. In the pad-dry-cold batch method, for example, after applying an aqueous solution, 50 to 11
Dry at a temperature of 0 ° C., then 20 at a temperature of 10-40 ° C.
Leave for ~ 40 hours. Among them, the dipping treatment method is preferable in terms of difficulty in rubbing during processing, processing effect, and feeling.

For dyeing, an acid dye or an alloy dye is used after the epoxy crosslinking. Reactive dyes are not preferred because they do not produce a dark color. For dyeing prior to epoxy crosslinking, acid dyes, alloy dyes, chromium dyes, slene dyes or reactive dyes are used.

[0017]

When a fiber structure made of silk fibers dyed in a dark color is treated with an epoxy at a high temperature when the fiber structure is treated with an alkali, a large amount of dye will cry out, but it can be prevented by the presence of sodium sulfate or sodium chloride. Sodium sulfate or sodium chloride acts as a swelling agent for silk fibers as well as a catalyst for crosslinking. The catalyst acts to crosslink the silk fibers with the epoxy compound, preventing fibrillation and preventing whitening.

It is believed that crosslinking of silk fibers with epoxy compounds occurs preferentially from hydroxyl groups of tyrosine.
If done prior to dyeing, it will interfere with the binding of reactive dyes,
Dark dyeing with reactive dyes after epoxy crosslinking is difficult. As for the catalyst used for epoxy crosslinking, the pH of the aqueous solution containing only the catalyst is less than 11, and when the pH of the aqueous solution containing the water-soluble polyfunctional epoxy compound and the catalyst is 9 or more, the crosslinking of silk is efficient. It is possible to prevent fibrillation and prevent whitening. If a catalyst which is contrary to this, such as zinc borofluoride or magnesium chloride, is used, the cross-linking efficiency of silk by the epoxy compound deteriorates, and it does not lead to whitening prevention.

[0019]

The present invention will be further described with reference to the following examples.
The invention is not limited by these examples. Each data in the examples was obtained as follows. (1) Alkali solubility indicates the solubility of silk fiber when a thread or socks made of silk fiber is immersed in a 5 wt% sodium hydroxide aqueous solution at 65 ° C. for 60 minutes. (2) Abrasion whitening was performed by rubbing a sample wet with water and dripping water with filter paper 100 times with a Martindale abrasion tester.
◯: No whitening, Δ: little whitening, ×: whitening was large. (3) Wearing whitening is the same person who wears athletic shoes every day and does almost the same work, wearing the product on one leg and the comparative product on the other foot for 5 hours. ○: No whitening, △: Little whitening , X: Evaluation was made with large whitening. (4) L value was used by colorimetry the L ^* a ^* b ^* color system of L ^* a Macbeth spectrophotometer.

Example 1, Comparative Example 1 A silk-preventing 60-count twin yarn was formed into a crease shape and dyed black with a reactive dye in a crepe dyeing machine, and then fixed and dyed black. Subsequently, using the same dyeing machine, an aqueous solution containing 20 g / l of ethylene glycol diglycidyl ether as an epoxy compound and 100 g / l of sodium sulfate as a catalyst (single pH 6.8) at a bath ratio of 1:50 (pH 11.
3) Immersion treatment was performed in 70 ° C. for 90 minutes. Further, oiling treatment was performed and knitted into men's socks (Example 1). For comparison, after black-dyeing, a sock for men's socks was knitted by oiling without epoxy compound treatment (Comparative Example 1).

Table 1 shows the alkali solubilities, abrasion whitening, wear whitening and L value of the products obtained in Example 1 and Comparative Example 1.

[0022]

[Table 1]

As is clear from Table 1, the product obtained in Example 1 has an alkali solubility of 30% by weight or less, and is free from abrasion whitening and wearing whitening despite being dyed in a dark color. .

Example 2, Comparative Example 2 Silk-spun 30th single yarn was made into a stripe shape and 20 g / l of glycerol diglycidyl ether as an epoxy compound and 100 g / l of sodium chloride as a catalyst (a single pH of 7. 0) in a bath ratio of 1:50 (pH 1
It was immersed in 1.1) at 90 ° C. for 60 minutes. Wash in hot water,
After washing with water, it was dyed with an alloy dye in the same dyeing machine, and then fixed and dyed in dark blue. Further, oiling treatment was performed and knitted into men's socks (Example 2).
For comparison, after dark blue dyeing without epoxy compound treatment,
A sock for men's socks was woven and subjected to oiling treatment (Comparative Example 2).

Table 2 shows the alkali solubilities, abrasion whitening, wear whitening and L value of the products obtained in Example 2 and Comparative Example 2.

[0026]

[Table 2]

As is clear from Table 2, the products obtained in the examples have an alkali solubility of 30% by weight or less, and it is clear that there is no abrasion whitening or wearing whitening even though they are dyed in a dark color.

Example 3, Comparative Example 3 Silk spinning 60-count double yarn was made into cheese and dyed with a reactive dye in a cheese dyeing Overmeier dyeing machine, and then fixed and dyed black. Subsequently, 30 g / l of propylene glycol diglycidyl ether as an epoxy compound and 100 g / l of sodium chloride as a catalyst.
Immersion treatment was carried out at 80 ° C. for 75 minutes in an aqueous solution (pH 11.0) containing (single pH 7.0). Further, oiling treatment was performed and knitted into men's socks (Example 3). For comparison, after black dyeing, an aqueous solution containing 50 g / l magnesium chloride (single pH 5.0) instead of sodium chloride (pH
When it was immersed in 8.7) at 80 ° C. for 75 minutes, the color fading was severe. Further, an oiling treatment was performed to make a knitted men's sock (Comparative Example 3). The black color of the comparative example was inferior in density to the black color of the example.

Table 3 shows the alkali solubilities, abrasion whitening, wear whitening and L value of the products obtained in Example 3 and Comparative Example 3.

[0030]

[Table 3]

As is apparent from Table 3, the product obtained in Example 3 has an alkali solubility of 30% by weight or less, and is free from abrasion whitening and wearing whitening despite being dyed in a dark color. .

[0032]

INDUSTRIAL APPLICABILITY As described above in detail, the fiber structure made of the silk fiber of the present invention is useful for men's socks and the like without wear whitening and wearing whitening even though it is dyed in a dark color. Is.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area // D06M 101: 12

Claims (3)

[Claims] 1. A 65% by weight 5% by weight aqueous sodium hydroxide solution.
Made of a silk fiber crosslinked with an epoxy compound having a solubility of 30% by weight or less when immersed at 60 ° C. for 60 minutes, L
A fiber structure made of silk fiber having a whitening resistance, which is characterized by being dyed with a value of 20 or less. 2. A fiber structure composed of silk fibers dyed with an L value of 20 or less is prepared by using an aqueous solution containing a water-soluble polyfunctional epoxy compound and one kind of catalyst selected from sodium sulfate or sodium chloride. A fibrous structure composed of silk fibers having whitening resistance, which is characterized by being immersed at a temperature of ℃ or less, or by being placed in a room temperature of 30 ℃ or less in a state where the above aqueous solution is applied to prevent evaporation of water. And its manufacturing method. 3. The pH of an aqueous solution containing only a water-soluble polyfunctional epoxy compound and a catalyst is 11 in a fiber structure made of silk fiber.
It is less than 10%, and a catalyst whose pH of an aqueous solution containing a water-soluble polyfunctional epoxy compound and a catalyst is 9 or more is applied, and then dyed with an acid dye or a metal-containing dye, and an L value is 20 or less. And a method for producing the same, which is made of silk fiber having whitening resistance.