JPH08158256A - Method for processing silk textile structural product - Google Patents

Abstract

PURPOSE: To obtain a silk textile structural product retaining its touch feeling inherent in silk fibers, hard to develop wrinkles thereon when worn, hard to run yellow, hard to develop friction marks thereon when washed, low in dimensional change, and hard to develop wrinkles thereon after washed, that is, wearable without the need of any ironing as well as endurable to mechanical washing. CONSTITUTION: This processing method is made up of the following two process: an original silk textile structural product is provided with an epoxy compound; and the resultant product is provided with urea and/or thiourea, dried, subjected to gaseous formaldehyde gas at >=100 deg.C in the presence of moisture, followed by exhaustion, and then further subjected to the formaldehyde gas with its partial pressure reduced to <=500mmHg. And at least the final drying is conducted by holding the product under low tension. Instead of the gaseous formaldehyde treatment, a reactive urethane resin may be imparted to the product.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing method for obtaining a silk fiber structure excellent in rubbing resistance, yellowing resistance, wrinkle resistance, and shrink resistance.

[0002]

2. Description of the Related Art A silk fiber structure has a unique texture and luster and is also excellent in mechanical properties such as strength and elasticity.
However, the silk fiber structure has the drawbacks that when it is used for clothing, it tends to wrinkle when worn and easily turns yellow, and also has the drawback that it easily rubs during washing and has a large dimensional change. There is a drawback that wrinkles tend to occur and they cannot be worn without ironing.

Various attempts have hitherto been made to prevent wrinkles from occurring in silk fiber structures, and many proposals have been made as shown below. (1) A liquid phase treatment method in which a bath liquid composed of various isocyanate-organic acid, urea-formalin, methylolacrylamide-stannic chloride is applied to cause a polymerization reaction in the fiber. (2) A gas phase treatment method in which a monomer vapor such as vinyl acetate, acrylonitrile, or formalin is applied in the presence of a catalyst. However, although such a treatment method provides wrinkle resistance, it has the drawback of being inferior in scratch resistance, yellowing resistance, wrinkle resistance, and shrink resistance.

On the other hand, various attempts have been made to prevent rubbing of silk fabrics, and methods using epoxides are known. For example, a method of pad dry-curing an epoxy compound with a catalyst selected from amine, acid and acid salt (Japanese Patent Publication No. 33-10654), an epoxide in contact with an alkali metal hydroxide or an alkaline salt of an alkali metal to form a pad. There are a dry steam method or a curing method (Japanese Patent Publication No. 38-25198), a method of treating with a cellulose-reactive crosslinking agent after epoxide treatment (Japanese Patent Laid-Open No. 62-231079) and the like. However,
Although such a treatment method provides anti-rub properties and anti-yellowing properties, it has the drawback of being inferior in wrinkle resistance and shrink resistance.

That is, the conventional processed silk fiber structure does not satisfy the four characteristics of rubbing resistance, yellowing resistance, wrinkle resistance, and shrink resistance.

[0006]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above problems, and does not change the unique texture of silk fibers, does not easily cause wrinkles when worn, and does not easily turn yellow.
Provided is a processing method capable of obtaining a silk fiber structure that is less likely to be rubbed during washing, has a small dimensional change, and is less likely to cause wrinkles after washing, that is, a silk fiber structure that can withstand machine washing and can be worn without ironing. The purpose is to do.

[0007]

To achieve the above object, the present invention has the following arrangement. That is, the first invention is
A step of applying an epoxy compound to the silk fiber structure, and applying urea and / or thiourea, and after drying, apply formaldehyde gas in the presence of water at a temperature of 100 ° C. or higher, and then exhaust. A method of processing a silk fiber structure is characterized by comprising a step of causing the gas to act under a gas partial pressure of 500 mmHg or less, and further maintaining at least the final drying under low tension. Of the present invention comprises a step of applying an epoxy compound to a silk fiber structure and a step of applying a reactive urethane resin, and further characterized in that at least the final drying is performed under low tension. The gist is the method of processing fiber structures.

The present invention will be described in detail below.

The silk fiber structure used in the present invention is not limited to a silk fiber alone, but may be a blend of silk and wool such as silk-wool, silk-polyester, silk-polyamide and various natural fibers, artificial fibers, or a mixed woven fabric. It means a woven fabric, a knitted fabric or a non-woven fabric.

The epoxy compound used in the present invention contains an epoxy group, and the water-soluble type is the most preferable in the process. Examples of such water-soluble epoxy compounds include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, sorbitol, polyglycerol, pentaerythritol, tris (2-hydroxyethyl) isocyanurate, trimethylolpropane, neopentyl glycol, phenol ethylene. Oxides, mono- and polyglycidyl ethers of lauryl alcohol ethylene oxide are mentioned. Polyglycidyl ethers such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, phenol ethylene oxide, lauryl alcohol ethylene oxide, glycerol and polyglycerol are preferred. In particular, ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether are preferable in terms of effects.

When ethylene glycol diglycidyl ether is used as the catalyst, sodium chloride, sodium sulfate, diethylenetriaminepentaacetic acid pentasodium and the like can be preferably used.

When the epoxy compound is applied to the silk fiber structure, a dipping heating method, a pad steam method, a pad dry steam method, a cold batch method or the like is applied. And, for example, in the cold batch method, 10 to 40 ° C.
It is left to stand for 20 hours or more and adheres, and it is 50 to 1 by the immersion heating method.
Heat-treated at 10 ℃ and fixed, 140-180 ℃ in pad steam method or pad dry steam method
Steam for 0.5 to 2 minutes to fix.

In the case of the padding method, the concentration of the epoxy compound aqueous solution or dispersion is preferably 70 to 400 g / l, more preferably 100 at a pickup rate of about 80%.
˜300 g / l, and in the case of the dipping method, it is preferably 5 to 50 g / l, more preferably 10 to 40 g / l. Such a concentration range is preferable in order to obtain both a sufficient rubbing prevention effect, a yellowing prevention effect and a soft texture.

When urea and / or thiourea is applied to the silk fiber structure, a pad dry method, a spray dry method or the like is applied. In the case of the padding method, the concentration of the urea and / or thiourea aqueous solution is preferably 20 to 100 g / l at a pickup rate of about 80%. Such a concentration range is preferable in order to obtain both sufficient wrinkle resistance and soft feeling. Inorganic metal salt-based catalysts, organic amine salt-based catalysts and the like can be preferably used as the catalyst.

In the reaction between urea or thiourea and formaldehyde, an addition reaction first occurs, and then a condensation reaction occurs, and then resinification proceeds. However, if the reaction does not proceed so much, naturally the wrinkle resistance is inferior and free formalin is formed. Will increase. Moisture is required to accelerate the addition reaction, and the subsequent condensation reaction is a dehydration reaction, and therefore the reaction can be promoted by removing the moisture out of the system.

First, the fiber structure is put into a treatment tank to cause an addition reaction, and the air partial pressure in the treatment tank before the addition of formamide gas is preferably 250 mmHg or less. If the air partial pressure in the treatment tank exceeds 250 mmHg, the whiteness and wrinkle resistance deteriorate.

The addition reaction is carried out by allowing formaldehyde gas to act at a temperature of 100 ° C. or higher in the presence of water, and the water content in the formaldehyde-water mixed gas is 1%.
0-100% is preferable. If the water content is less than 10%, the reaction takes time and the wrinkle resistance is poor, and if the water content exceeds 100%, the subsequent condensation reaction is difficult to proceed and the wrinkle resistance is deteriorated. The temperature of the gas phase treatment is 100% or more, preferably 100 to 135 ° C.
For about 30 to 120 minutes. It should be noted that this treatment condition embrittles the silk fiber when the temperature is too high and long.

Next, in the condensation reaction system, water is removed, but the gas partial pressure in the reaction system is reduced to 500 mmHg or less, preferably 300 mmHg or less. By repeating this depressurization operation once or more, resinification is promoted, and wrinkle resistance is excellent and free formalin becomes small. After the gas phase treatment, soaping is performed to wash off formaldehyde, and then dried.

As the reactive urethane resin used in the present invention, specifically, Viplet USV (manufactured by Bayer),
Elastron MF-9 (manufactured by Daiichi Kogyo Co., Ltd.), Elastron MF-25 (manufactured by Daiichi Kogyo Co., Ltd.) and the like can be mentioned. When applying the reactive urethane resin to the silk fiber structure, a pad dry method, a spray dry method, a coating dry method or the like is applied. In the case of the padding method, the concentration of the aqueous solution of the reactive urethane resin is 20 to 2 depending on the effective component of the reactive urethane resin when the pickup rate is about 80%.
00 g / l is preferred. Such a concentration range is preferable in order to obtain both sufficient wrinkle resistance and soft feeling.

More importantly in the present invention is the drying in the final resin application, or when the resin is fixed and then moistened with water or an aqueous liquid for drying, that is, at least the final drying step is performed on the silk fiber structure. It is to keep it under low tension and dry it. Specifically, drying under low tension
For example, when the fiber structure is supplied to the dryer, it is possible to detect the shrinkage amount or supply unevenness of the fiber structure and change the supply speed, or to supply the fiber structure by using an air flow. Is mentioned. Also, the drying process requires high caution because it tends to become high tension due to the drying shrinkage effect of the fiber structure,
It is important to carry out the process more slowly than usual. As such a drying device, a short loop dryer, a net dryer, or an ager machine modified as described above is preferable. By these treatments, the silk fiber structure undergoes sufficient shrinkage and becomes dimensional stable.

The present invention will be specifically described below with reference to examples. In addition, the following methods were used for rubbing prevention property, yellowing prevention property, wrinkle prevention property, W & W property and shrinkage resistance, and the evaluation was ◯: good, Δ:
Slightly bad, ×: It was bad. (1) Anti-rubbing property ... Washing according to JIS L 0217
According to Method 105 (however, bathing 1: 300), the degree of fibrillation was evaluated by the visual judgment of 10 specialist inspectors by air drying and an electron micrograph. (2) Anti-yellowing property: Performed according to JIS L 0842, and the yellowing degree after irradiation for 60 hours was evaluated by visual inspection by 10 expert inspectors. (3) Wrinkle resistance: A 5 hour wear test was conducted, and then 1
The evaluation was made by the visual judgment of 0 professional inspectors. (4) W & W property: AATCC method (drip dry)
The evaluation was performed according to the method, and then evaluated by visual judgment by 10 professional inspectors. (5) Shrinkproof property ... Washing according to JIS L 0217 10
The method was carried out according to Method 5 (however, bathing 1: 300), and after air-drying, the shrinkage ratio was measured.

Example 1 As an epoxy compound, ethylene glycol dichrysidyl ether (Denacol EX810, manufactured by Nagase Kasei Co., Ltd.)
20 g / l, 100 g / l of sodium sulfate as a catalyst for an epoxy compound and water were adjusted to one bath in a jigger, and the scoured and bleached warp and weft yarns of Fuji silk using 100-count twin yarn were soaked at 90 ° C. It was heat-soaked for 60 minutes, then washed with water and dried.

Urea 50 g / l, metal salt catalyst as a catalyst (Sumitex Accelerator KX, manufactured by Sumitomo Chemical Co., Ltd.) 15
g / l and water were adjusted to one bath. Then, the Fuji silk treated with the epoxy compound was dipped, squeezed to 80% with a mangle, and dried at 120 ° C. for 1 minute. Next, the urea-treated Fuji silk was placed in a closed treatment tank, and the air partial pressure in the treatment tank was adjusted to 20%.
The pressure was reduced to 0 mmHg, formaldehyde gas containing 30% of water was added, and after reacting at 120 ° C. for 1 hour, the pressure inside the treatment tank was reduced to 300 mmHg, and then 1
After left for a period of time, remove the sample from the treatment tank and use Marcel's soap 0.2% and ammonia 0.1% solution at 60 ° C for 10 hours.
It was soaped for a minute, washed with water and dried.

Aminosilicon type softening agent (Texasilicon OP81N, manufactured by Osaka Chemical Co.) as a softening agent 30 g /
1 and water were adjusted to one bath. After soaking Fuji silk treated with vapor-phase formalin and squeezing it to 80% with mangle, the length of the cloth is measured by controlling the photoelectric tube to form a constant loop, and the nip roll is driven by a torque motor to form a short loop. A short loop that is formed and sent onto the conveyor, and further provided with a jet air nozzle along the cloth width at the entrance of the dryer to prevent the loop from returning, applying wind pressure from above the dryer against the wind pressure from below the dryer. The product of Example 1 was obtained by low tension drying for 2 minutes at 120 ° C. using a dryer.

Comparative Example 1 Comparative Example 1 was carried out in the same manner as in Example 1 except that the drying after applying the aminosilicone-based softening agent was performed using a pin tenter instead of the short loop dryer. 1 product was obtained.

Comparative Example 2 A product of Comparative Example 2 was obtained by performing the same processes as in Example 1 except that the gas phase formalin treatment was not carried out.

Comparative Example 3 A product of Comparative Example 3 was obtained by performing the same processes as in Example 1 except that the epoxy compound treatment was not carried out.

Table 1 shows the manufacturing process of the products obtained in Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3, and the rubbing preventive property, yellowing preventive property, wrinkle preventive property, and shrink preventive property.

[0029]

[Table 1]

As is clear from Table 1, the products obtained in the examples are excellent in rubbing resistance, yellowing resistance, wrinkle resistance, and shrink resistance.

Example 2 As an epoxy compound, ethylene glycol dichrysidyl ether (Denacol EX810, manufactured by Nagase Kasei)
30 g / l, 100 g / l of sodium sulfate as a catalyst for epoxy compound and water were adjusted to one bath in a jigger, and scouring and bleaching were carried out by a conventional method, and 100-count twin-threaded Fuji silk was soaked at 90 ° C. It was heat-soaked for 60 minutes, then washed with water and dried.

Reactive urethane resin (Viplet US
V, manufactured by Bayer Co., active ingredient 30%) 100 g / l, aminosilicone softening agent (Texasilicon O as a softening agent)
P81N, manufactured by Osaka Chemical Co., Ltd.) 30 g / l, and water were adjusted to one bath. Then, Fuji silk treated with an epoxy compound was dipped, squeezed to 80% with a mangle, and then dried. Next, using an ager, heat treatment was performed at 130 ° C. for 8 minutes under free tension.

Furthermore, Fuji silk treated with a reactive urethane resin was dipped in water, squeezed to 80% with a mangle, and then the length of the cloth was measured by controlling a photoelectric tube to form a constant loop.
A nip roll is driven by a torque motor to form a short loop and sent to the conveyor.Furthermore, a jet air nozzle is installed along the width of the dryer at the dryer inlet to prevent the loop from returning and to resist wind pressure from under the dryer. The product of Example 2 was obtained by low tension drying for 2 minutes at 120 ° C. using a short loop dryer in which wind pressure was applied from above.

Comparative Example 4 Comparative Example 4 was carried out in the same manner as in Example 2 except that the reactive urethane resin was not used, only the amino-modified silicone softener was used, and no heat treatment was performed with an ager. 4 products were obtained.

Comparative Example 5 A product of Comparative Example 5 was obtained by performing the same processes as in Example 2 except that the epoxy compound treatment was not carried out.

Comparative Example 6 In Example 2, the heat treatment after applying the reactive urethane resin was performed at 150 ° C. for 3 minutes with a baking machine under tension to obtain a final product (after passing water, in a short loop dryer). The same treatment as in Example 2 was carried out except that it was not dried) to obtain a product of Comparative Example 6.

Table 2 shows the manufacturing process of the products obtained in Example 2, Comparative Example 4, Comparative Example 5 and Comparative Example 6 and the anti-rub property, anti-yellowing property, wrinkle-proof property, W & W property and shrink-proof property. .

[0038]

[Table 2]

As is clear from Table 2, the products obtained in the examples are excellent in rubbing resistance, yellowing resistance, wrinkle resistance, and shrink resistance.

[0040]

As described in detail above, according to the method of the present invention, wrinkles are less likely to occur during wearing, yellowing is less likely to occur, and rubbing occurs during washing, without changing the unique texture of knitted fibers. It is difficult to obtain a silk fiber structure that is small in dimensional change and less likely to cause wrinkles after washing, that is, a silk fiber structure that can withstand machine washing and can be worn without a iron, and is extremely useful as a shirt / blouse application. Therefore, it can be applied to applications where the silk fiber structure cannot be used conventionally. Further, the method of the present invention can be carried out by using a conventional apparatus, and its usefulness is obvious.

Claims (2)

[Claims] 1. A process of applying an epoxy compound to a silk fiber structure, and a process of applying urea and / or thiourea and drying, and then applying formaldehyde gas at a temperature of 100 ° C. or higher in the presence of water. After that, exhaust and gas partial pressure is 500mm
A method for processing a silk fiber structure, which comprises a step of causing the composition to act under a condition of Hg or less, and further holds at least the final drying under low tension. 2. A silk fiber structure comprising a step of applying an epoxy compound and a step of applying a reactive urethane resin, wherein at least the final drying is carried out under a low tension. Method of processing silk fiber structure.