JPH06166955A - Shrink-proof finishing of cellulosic fiber cloth - Google Patents

Abstract

PURPOSE:To obtain a cloth having low free formaldehyde content and excellent shrink-proofness by crosslinking a rayon fiber cloth in a specific state and subjecting the cloth to low-temperature plasma treatment. CONSTITUTION:A cellulosic fiber cloth, especially a rayon fiber cloth is immersed in a treating liquid containing a crosslinking agent (e.g. methylol-type resin), preferably a non-formaldehyde crosslinking agent and a catalyst, and dried in a state pressed in longitudinal direction with a compressive processing machine to effect the crosslinking reaction with the crosslinking agent. The crosslinked cloth is subjected to low-temperature plasma treatment to obtain the objective cellulosic fiber cloth having excellent shrink-proofness.

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 imparting shrink-proof property to withstand washing and washing to a cellulosic fiber cloth and suppressing the amount of free formaldehyde to a low level.

[0002]

2. Description of the Related Art Cellulose fiber cloths, especially rayon fiber cloths, have the property of swelling greatly when wetted with water and remarkably shrinking when dried, and therefore cannot be washed with water. In order to prevent this, as a shrink-proofing method for cellulosic fibers, conventionally, a method has been used in which a film is formed by using a polyurethane resin or the like, and shrink-proofing is imparted by restraining the movement of the fiber, urea formalin resin, and methylol. A method is generally known in which a crosslinking agent such as a melamine resin or a glyoxal-based resin is used to crosslink the molecules to suppress the degree of freedom of the cellulose molecule itself to impart shrinkage resistance.

[0003]

The N-methylol compound uses formaldehyde to form a methylol group and releases formaldehyde when an unreacted cross-linking agent remains on the cloth. Especially, rayon fiber cloth is It releases more formaldehyde than other cellulosic fiber fabrics. Even if the amount of the cross-linking agent is reduced or the formalin catcher agent is used, the amount of free formaldehyde does not decrease so much as compared with the degree of deterioration in performance. Therefore, the conventional shrink-proof rayon fiber cloth cannot be used for clothing.

The present invention has been made in view of the above circumstances, and is a processing method for imparting shrink-proofing ability to withstand washing with water to a cellulose fiber cloth, particularly rayon fiber cloth, and suppressing the amount of free formaldehyde to a low level. The first purpose is to obtain.

It is a second object of the present invention to obtain a processing method for imparting shrink-proof property which does not generate free formaldehyde and can withstand washing and washing to a cellulosic fiber cloth, particularly rayon fiber cloth.

[0006]

SUMMARY OF THE INVENTION The present invention achieves the above object and has the following configuration.

[0007] That is, the first invention of the present application is that "the cellulosic fiber cloth is impregnated with a treatment liquid containing a crosslinking agent and a catalyst, and dried in a state where it is compressed in a longitudinal direction by a compression processor, and the crosslinking reaction of the crosslinking agent is carried out. The second invention of the present application is "a low-formaldehyde shrink-proofing method for a cellulosic fiber cloth, which is characterized by performing a low-temperature plasma treatment after that." Cellulosic fiber characterized by being impregnated with a treatment liquid containing a cross-linking agent and a catalyst, dried in a state compressed in a longitudinal direction by a compression processing machine, and then subjected to a cross-linking reaction of the cross-linking agent, followed by low-temperature plasma treatment. The non-formaldehyde shrink-proofing method of cloth "is the gist.

The present invention will be described in detail below.

In the method of the present invention, a cellulosic fiber cloth is used as an object to be processed. The term “cellulosic fiber cloth” as used herein means a woven fabric or knitted fabric made of fibers such as cotton, hemp, and rayon. Particularly, when a woven fabric or knitted fabric made of rayon fiber is used as a fabric to be processed, the shrinkproof effect of the present invention is obtained. Is most effective because it appears remarkably.

In the method of the present invention, first, the above-mentioned cellulosic fiber cloth is impregnated with a treatment liquid containing a crosslinking agent and a catalyst.

The cross-linking agent used in the present invention is a general resin finishing agent for ordinary cellulose fibers such as N-methylol resin and aldehydes.

The catalyst used in the present invention is a catalyst suitable for each cross-linking agent such as free acid, ammonium salt (ammonium chloride) amine salt, metal salt (magnesium chloride, zinc nitrate, zinc borofluoride, sodium carbonate). Can be used.

The amount of the cross-linking agent used in the present invention is
The resin solid content is preferably about 4 to 8% by weight with respect to the fiber weight. If the amount of the cross-linking agent is less than 4% by weight, sufficient shrink-proof performance cannot be obtained, and even if the cross-linking agent is added in excess of 8% by weight, the shrink-proof performance tends to be no longer improved. It is an economy.

When the processed fabric does not contain free formaldehyde, a non-formalin resin, an epoxy resin, an imidazoline resin as a crosslinking agent,
It is recommended to use a general resin finishing agent for cellulosic fibers which does not contain formaldehyde such as polycarboxylic acid and sulfone compound.

In this case, the amount of the cross-linking agent applied is preferably about 6 to 12% by weight of the resin solid content with respect to the weight of the fiber. If the amount of the cross-linking agent is less than 6% by weight, sufficient shrinkproof performance cannot be obtained, and even if it exceeds 12% by weight, the shrinkproof performance tends to be no longer improved, which is uneconomical.

In order to impregnate the cellulosic fiber cloth with the treatment liquid, the fabric is dipped in the treatment liquid using a mangle and the liquid is squeezed with a squeezing roll in the range of 50 to 120% of the pickup.

After impregnating the cloth with the treatment liquid, in the present invention, the cloth is dried in a state of being compressed in the warp direction by a compression processor to crosslink the crosslinking agent.

As the compression / shrinking machine, a "Sunforised" finishing machine (manufactured by Sunforised) and a cam fit machine (manufactured by Uenoyama Kiko Co., Ltd.), which utilizes expansion and contraction of a rubber belt, "Bestan". (Hunt & Moscrop Co.) or "Compacter" (Tub-Tex Co.) typified by passing between two rollers and using the difference in surface speed between the two rollers. You can

The compression / shrinkage rate by the compression / shrinkage machine at the time of drying is set to about 2 to 5%, and it is carried out at 100 to 120 ° C. for 1 to 2 minutes while physically adding the density. To carry out the crosslinking reaction of the crosslinking agent, dry heat or wet heat treatment is performed. In the case of dry heat treatment, it is performed at 150 to 170 ° C. for 1 to 2 minutes. In this case, if the temperature is 150 ° C. or lower, the crosslinking reaction becomes insufficient, so that satisfactory shrink-proofing performance cannot be obtained, and if the temperature is 170 ° C. or higher, the fabric is hardened, yellowed, and the strength is lowered.
When performing heat-moisture treatment, use a steamer for 160 to 1
Perform at 80 ° C. Also in this case, if the temperature is 160 ° C. or lower, the crosslinking reaction is insufficient, and if the temperature is 180 ° C. or higher, the fabric is hardened, yellowed, and the strength is lowered, which is not preferable either.

Next, in the method of the present invention, the low temperature plasma treatment is performed on the resin-processed cellulosic fiber cloth. The low-temperature plasma processing device used at this time has an electrode for discharge in a vacuum container that can maintain a low pressure, a specific gas can be introduced at a predetermined flow rate, and the inside of the container is evacuated by an attached vacuum pump. It is a device that has a structure and performance capable of maintaining a constant pressure. When a voltage is applied to the electrodes in this device, glow discharge occurs and low temperature plasma is formed.
Most commonly, high frequency power of 13.56 MHz is applied. The low temperature plasma treatment can be performed by passing the cellulosic fiber cloth to be treated at a desired speed in a low temperature plasma atmosphere formed between the electrodes.

In the case of the present invention, the gas used at this time is
Any non-polymerizable gas such as oxygen, nitrogen, air, argon, or helium, or a mixed gas thereof may be used.
It may be a polymerizable gas such as tetrafluoromethane and is not particularly limited.

First, a cellulosic fiber cloth is housed in a vacuum container and evacuated by a vacuum pump to reduce the internal pressure to 0.0.
The pressure in the container is adjusted to 0.1 to 5 Torr, preferably after adjusting the pressure in the container to 1 to 1 Torr, and then introducing the above-mentioned gas such as oxygen gas into the container to replace residual air. adjust. Then, high-frequency power is applied to the electrodes to cause glow discharge, so that the introduced gas becomes a low-temperature plasma state. The high frequency power at this time is 0.1 to 0.5 W / cm ²
(Electrode unit area) is suitable. The low-temperature plasma treatment is performed by passing the cellulosic fiber cloth previously stored in this low-temperature plasma atmosphere. The processing time at this time is usually several seconds to 300 seconds, preferably 30 to 180 seconds.
Seconds.

By carrying out the above-mentioned processing, it is possible to obtain a cellulosic fiber cloth having a low amount of free formaldehyde, which is unprecedented in the present invention, or having high shrinkage resistance and containing no free formaldehyde.

[0024]

[Operation] Generally, a cross-linking agent restrains the movement of cellulose molecules and imparts shrink-proof property to the fiber, but unreacted cross-linking agent, acid catalyst, etc. remain to release formaldehyde. When the cellulose fiber is impregnated with a cross-linking agent as in the method of the present invention, and then the cross-linking reaction is performed in a compressed state in a wet state, the cellulose molecules are cross-linked in a reasonable state, so that excellent shrink-proofing performance can be obtained. . Also, by physically adding the density, it becomes possible to obtain good shrinkproofing performance even with a resin solution having a low concentration.

Further, when low-temperature plasma treatment is carried out as in the present invention, the crosslinking force between resins is further enhanced, the shrinkage prevention effect is further enhanced, and the resin which has not reacted in the heat treatment acts to crosslink, thereby reducing the amount of free formaldehyde. .

Further, the formaldehyde-free cross-linking agent used in the second invention of the present application has a weak force for restraining the movement of cellulose molecules and does not have a sufficient shrink-proof property. After the agent is impregnated, it is compressed and contracted in a wet state, and when the cellulose molecules are cross-linked by a chemical treatment and then low-temperature plasma treatment is performed, the cross-linking force between the resins is further enhanced, and the shrinkage prevention effect is further enhanced, and free formaldehyde It becomes possible to provide the rayon cloth with shrink-proofing performance that does not include

[0027]

EXAMPLES The present invention will be described in more detail with reference to examples below. The performance of the fabrics in the examples was measured by the following method. (1) Shrink resistance JIS L-0217 103 method (10 times of washing, tumble dry 60 ° C x 20 minutes) (2) Tear strength JIS L-1018 Pendulum method (3) Free formalin amount JIS L-1041 Acetylacetone method

Example 1 A 100% rayon woven fabric (warp 100d, weft 30s, warp density 107 yarns / inch, weft density 66 yarns / inch) dyed and finished by a conventional method was prepared. It was impregnated with the above resin solution and squeezed with mangle at a squeezing rate of 70%.

[Formulation 1] Sumitex Resin NS-11 150 g / liter (Sumitomo Chemical Co., Ltd., low formaldehyde shrink-proofing agent) Sumitex Accelerator X-1 10 45 g / liter (Sumitomo Chemical Co., Ltd., catalyst) Riken Sofner S-604 30g / l (Miki Riken Kogyo Co., Ltd., softening agent) Polon MF-5 20g / l (Shin-Etsu Chemical Co., Ltd., silicone resin)

Next, a cam fit processing machine (manufactured by Shandong Iron Works Co., Ltd.) was used to perform compression shrinkage processing of 3.5% in the warp direction of the woven fabric under the condition of a rubber temperature of 120 ° C.

Subsequently, after drying at 120 ° C. for 1 minute with an overfeed of 3%, dry heat treatment was performed at 170 ° C. for 1.5 minutes. After that, low temperature plasma treatment was performed under the following low temperature plasma treatment condition 1 to obtain a work cloth of the present invention.

[Low-temperature plasma treatment condition 1] Gas species: Oxygen gas flow rate: 0.2 liter / min Vacuum degree: 1.0 Torr High frequency output: 0.5 KW Treatment time: 1 minute

For comparison with the present invention, a comparative woven fabric subjected to only resin processing and compression / shrink processing according to the above formulation 1 (Comparative Example 1), and a woven fabric subjected to only resin processing according to the above Formulation 1 (Comparative Example 2) , And a comparative woven fabric that was only bleached (Comparative Example 3).

The shrink resistance, tear strength and amount of free formalin were measured for the present invention and the comparative woven fabric, and the results are shown in Table 1.

[0035]

[Table 1]

As is clear from Table 1, the processed cloth according to the present invention had a good shrink-proofing effect, and the free formalin content was suppressed to a low level range.

Example 2 The process of the present invention was carried out in the same manner as in Example 1 except that the following Formulation 2 using a nonformaldehyde-based shrinkproofing agent was used in place of Formulation 1 in the above Example 1. Got a cloth.

[Formulation 2] Thermoresin FG-450 200 g / liter (manufactured by Hiramatsu Yushi Co., Ltd., non-formaldehyde shrink-proofing agent) Catalyst HG-50 60 g / l (manufactured by Hiramatsu Yushi Co., Ltd., catalyst) Sumitex Softener LK- 1 30 g / liter (Sumitomo Chemical Co., Ltd., softener) PORON MF-5 20 g / liter (Shin-Etsu Chemical Co., Ltd., silicone resin)

For comparison with the present invention, a comparative woven fabric subjected to only resin processing and compression / shrink processing according to the above formulation 2 (Comparative Example 4), and a woven fabric subjected to only resin processing according to the above Formulation 2 (Comparative Example 5) , And a comparative woven fabric that was only bleached (Comparative Example 6).

The shrink resistance, tear strength and amount of free formalin of the present invention and the comparative fabric were measured, and the results are shown in Table 2 together.

[0041]

[Table 2]

As is clear from Table 2, the processed cloth according to the present invention has a good shrink-proof effect, no reduction in strength, and no free formalin was detected.

[0043]

According to the present invention, it is possible to produce a rayon cloth having good shrink resistance and a small amount of free formalin. Further, according to the present invention, it is possible to produce a rayon cloth having good shrink-proof performance without using formalin.
Clothing made of these rayon fabrics is particularly suitable for summer clothing because it can be washed by washing with water at home.

Claims (2)

[Claims] 1. A cellulosic fiber cloth is impregnated with a treatment liquid containing a cross-linking agent and a catalyst, dried in a state of being compressed in a longitudinal direction by a compression processor, and a cross-linking reaction of the cross-linking agent is performed, followed by low-temperature plasma treatment. A low-formaldehyde shrinkage-proofing method for a cellulosic fiber cloth, which comprises applying the method. 2. A cellulosic fiber cloth is impregnated with a treatment liquid containing a non-formaldehyde type crosslinking agent and a catalyst, dried in a state of being compressed in a longitudinal direction by a compression processor, and a crosslinking reaction of the crosslinking agent is carried out, followed by low temperature. Characterized by plasma treatment,
A non-formaldehyde shrink-proofing method for a cellulosic fiber cloth.