JPH0641668B2 - Resin processing method for silk fiber products - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin processing method for silk fiber products.

BACKGROUND ART A large number of resin processing agents that react with silk fibers have been developed for the purpose of permanent modification of silk fibers. Examples of processing agents that have been put into practical use include amino resins, epoxy resins, and ethyleneimine-based resins. , Urethane resins, esterification resins and the like are known.

In order to modify the physical properties of fibers by allowing a reactive resin finishing agent of this kind to act on silk fibers, the following methods are generally adopted.

a) Fibers are impregnated with a treatment liquid (aqueous solution, emulsion or organic solvent solution) containing a resin processing agent, and pre-dried and heat-treated.

b) The reaction is performed while the fibers are immersed in the treatment liquid.

c) A fiber having an appropriate amount of water and a solution of a resin-treating agent in a poorly water-soluble organic solvent are thermally reacted.

In the case of a) above, the step of heat treatment in which a covalent bond is formed between the fiber and the resin-treating agent is a solid phase for both the fiber and the resin-treating agent.
Alternatively, the reaction is a two-phase system in which the fiber is the solid phase and the resin processing agent is the liquid phase. In such a method, the resin moves along with the volatilization of the solvent during the steps of preliminary drying and heat treatment, so that the concentration distribution of the resin processing agent becomes nonuniform, and the modification effect is likely to be uneven. In addition, since the contact between the two is limited in the two-phase reaction,
Generally the reaction rate is slow.

Further, in the case of b), water competes with the functional group on the fiber in the reaction with the resin processing agent, and therefore, when water is present, a part of the processing agent reacts with water and is transformed into a reagent that does not react with the fiber.
In order to avoid this, there is an example in which the reaction is carried out in an organic solvent [Journal of the Fiber Society of Japan, Vol. 42, T152 (1986)], but also in these cases, the main purpose is to use the resin processing agent as a solution, and improvement in reaction rate and the like. It is not allowed.

Further, as an example of c), a two-phase system of water-poorly water-soluble organic solvent is found in Japanese Patent Publication No. 52-38131, but in this case, the reaction takes a long time.

As described above, when the reaction between the resin processing agent and the fiber is slow, or when the local concentration of only the resin processing agent is high, the condensation of the resin processing agents may occur. When the self-condensation product of the resin processing agent has a large molecular weight and is subjected to heat treatment to be deposited on the fiber, it is generally difficult to remove it. Further, it is considered that light-white stains cannot be removed only by washing if the molecular weight exceeds 10,000 [Jap. Of Japan Oil Chemistry, Vol. 36, page 754 (1987)]. In addition, resinous agent self-condensed deposits generally harden the fibers and result in reduced tear strength.

The present invention is a method of efficiently reacting such a resin-treating agent with silk fibers, and effectively modifying the physical properties of silk fiber products without substantially adversely affecting the original texture and strength of the fibers. The challenge is to provide.

Means for Solving the Problems As a result of earnest research, the present inventor has found that a resin-processing agent reactive with silk fiber was treated with silk in the presence of a quaternary ammonium salt or an amine oxide in an aprotic polar solvent. It has been found that by impregnating a fiber product and heat-treating it under the condition that solvent volatilization is suppressed as much as possible, the silk fiber can be reacted quickly and the intended problem can be solved.

Since the aprotic polar solvent has a high swelling property for the fiber, when the resin processing agent is reacted in the presence of the aprotic polar solvent, the swelling of the fiber facilitates the reaction inside the fiber, and the resin The self-condensate of the processing agent remains without depositing on the fiber surface and can be easily removed in the washing step. Therefore, in the present invention, an excellent resin processing effect can be obtained without damaging the original physical properties of the silk fiber. Obtainable.

Further, in the reaction between the silk fiber-reactive resin-treating agent and the silk fiber, the functional groups such as hydroxyl group, amino group, carboxylic group, and mercapto group on the silk fiber react with the resin-treating agent as a nucleophile, but non-proton Since a polar polar solvent selectively solvates the cations of an ion pair, the anion (generally a nucleophile) becomes almost naked and its nucleophilicity is significantly increased. Therefore, an aprotic polar solvent is used. Exerts the effect of significantly increasing the reactivity of this nucleophile, that is, the functional group on the silk fiber.

Further, since the aprotic polar solvent generally has a high boiling point, it is possible to prevent volatilization of the solvent at the heat treatment temperature of the resin processing agent by a simple means, prevent migration of the resin processing agent, and prevent uneven modification effect. In addition, since the aprotic polar solvent has a high solubility in the resin processing agent, it is possible to prepare a high-concentration resin processing agent solution, and a sufficient amount of the resin processing agent can be prepared by one-time impregnation. There is also an advantage that it can be given to.

An aprotic polar solvent is generally considered to have a dielectric constant of 15 or more, but in the present invention, it is preferable to use an aprotic polar solvent having a dielectric constant of 29 or more. In addition, it is preferable to use one having a boiling point of 100 ° C. or higher.

Aprotic polar solvents useful in the present invention include acetonitrile, dimethylformamide, dimethylsulfoxide, methylethylsulfoxide, hexamethylphosphoramide, nitromethane, dimethylacetamide, sulfolane, N-methylpyrrolidone and the like. These may be used as a mixture, or may be used by adding a small amount of water, a known resin processing agent, a softening agent, a penetrating agent, or the like.

In the present invention, in such an aprotic polar solvent, for example, amino resin, epoxy resin, ethyleneimine resin,
A silk fiber product is resin-processed using a treatment liquid containing a resin-processing agent reactive with silk fibers such as urethane resin and esterification resin together with a so-called phase transfer reaction catalyst.

Further, the resin processing of the present invention is carried out in the presence of quaternary ammonium salts or amine oxides, but these compounds function as so-called phase transfer reaction catalysts, and are used in aprotic polar solvents. However, when a small amount of these compounds is added, the reaction between the resin processing agent and the fiber is promoted, and the modifying effect of the resin processing agent is remarkably increased.

This is because in the present invention, a two-phase system reaction between the solid phase fiber and the liquid phase aprotic polar solvent solution is progressing, and this heterogeneous reaction promotes the solid-liquid interface reaction, that is, the interphase reaction. It is believed to be promoted by the transfer reaction catalyst.

The reactive resin processing agent is preferably used in a proportion of 0.1 to 12% by weight based on the silk fiber product which is the object to be treated,
Further, the above compound that promotes the solid-liquid interface reaction is preferably used in an amount of about 0.05 to 5% by weight of the resin processing agent.

A general resin processing catalyst may be used in combination with the treatment liquid.

Impregnation of the treatment liquid into the silk fiber product may be carried out by a dipping method, a padding method, a coating method, etc., but in the subsequent heat treatment, that is, the reaction step, the aprotic polar solvent does not evaporate (the reaction is It is important to be carried out under the condition that the reaction proceeds in an aprotic polar solvent).
Since the boiling point of the aprotic polar solvent is relatively high, the heat treatment temperature can be set to an appropriate temperature below the boiling point even in an open state to achieve the intended purpose. The product may be heated in a closed container or wrapped in a film or the like and heated.

As the heat treatment method, any heat source such as hot air, infrared rays, microwaves, and steam may be used. The number of heat treatments is not limited, but the preferable heat treatment temperature is 50 to 19
The temperature is 0 ° C., and the preferable treatment time is 1 to 30 minutes. The heat treatment conditions may be appropriately selected such that the resin processing agent is fixed to the cloth and the cloth is not damaged.

After the heat treatment, washing is preferably performed to remove the non-fixed portion in the cloth.

The silk fiber product processed in the present invention may be made of silk fiber alone, or may be made of a mixed-spun or interwoven fabric of silk fiber and other fibers. The shape of the textile product may be any of yarn, woven fabric, knitted fabric, non-woven fabric, sewn product and the like. Furthermore, these may be previously processed with other processing agents within a range that does not interfere with the processing of the present invention.

Next, examples will be shown. The materials used in the examples and the methods for measuring physical properties are as follows.

Materials used in Examples 1) Test cloth Silk (palace crepe): 3 out of 21 warp plain threads 4 out of weft 21 3,200 t / m (twisting constant 2.9 x 10 ⁵ ) Silk (Ichikoshi Chirimen): Warp 21 out of 21 3 plain yarns 14 out of 21 wefts 3,200t / m (twisting constant 4.0 x 10 ⁵ ) Silk (satin crepe): 3 out of warp 21 plain yarns 6 out of 21 wefts (3,500t / m, 600t / m) 2) Resin Processing agents and commercial catalysts therefor 3) Catalyst according to the present invention (compound that accelerates reaction at solid-liquid interface) Tetra-n-butylammonium bromide (Quaternary ammonium salt-special grade reagent of Wako Pure Chemical Industries, Ltd.-abbreviated as TBAB hereinafter) Dimethyl Dodecylamine oxide (Amine oxide synthesized from dimethyllaurylamine and H ₂ O ₂ , hereinafter abbreviated as DDAO) 4) Solvent water Dimethyl sulfoxide (Special grade reagent manufactured by Wako Pure Chemical Industries, Ltd., abbreviated as DMSO hereinafter) Dimethylformamide (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as DMF) 5) Other reagents Sodium carbonate (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) Nonipol # 200 (Sanyo Chemical Co., Ltd.) Non-ionic surfactant) Physical property measurement method 1) Resin adhesion rate 2) Wrinkle prevention rate (%) Measured according to JIS L 1095-85 B method (Monsanto method).

3) Hand Bending Property Bending rigidity B (g · cm ² cm) and bending hysteresis (g · cm / cm) were measured according to the KES method bending property test.

4) Shrinkage (%) Measured according to JIS L 1042-83 B method.

5) Alkali resistance The weight loss rate (%) of the test cloth when the test cloth was immersed in a 1N-NaOH aqueous solution at 25 ° C. for 10 minutes was shown.

6) The yellowing resistance test cloth is irradiated with ultraviolet rays for a predetermined time by a fade meter (manufactured by Suga Test Instruments Co., Ltd.), and the X, Y, Z values at that time are measured by a color computer (manufactured by Suga Test Instruments Co., Ltd.). From this, the yellowing degree ΔY1 was calculated.

Example 1 DMSO containing 30% by weight of resin processing agent and 3% by weight of catalyst
A solution and an aqueous solution were prepared, and a test cloth (palace crepe) was dipped in the solution and squeezed at a draw ratio of about 90%.

Then, the one soaked in the aqueous solution was dried at 80 ° C. for 3 minutes and heat-treated, and the one soaked in the DMSO solution was directly heat-treated as it was, and then sodium carbonate and nonipol # 2
It was soaped with a hot aqueous solution containing a small amount of 00, thoroughly washed with hot water and washed with water, and then dried.

By changing the types of resin processing agents and catalysts used and the heat treatment temperature as shown in Table 1, the resin adhesion rate on the processed cloth
(%) Were compared. The results are shown in Table 1. The heat treatment time was 5 minutes.

From the results of Table 1, according to the present invention, an aprotic polar solvent (DMSO) and a catalyst (TB that promotes solid-liquid interface reaction)
It can be seen that the adhesion rate of the resin processing agent to the fibers is remarkably excellent when (AB and DDAO) is used as compared with the case where water is used as a solvent and the case where a general metal catalyst is used as a catalyst. .

Example 2 A DMF solution and an aqueous solution containing 30% by weight of a resin processing agent and 3% by weight of a catalyst were prepared, and a test cloth (Ichikoshi crepe or Suzaku crepe) was dipped in the solution and squeezed at a squeezing ratio of about 90%. .

Then, the one soaked in the aqueous solution was dried at 80 ° C. for 3 minutes and heat-treated, and the one soaked in the DMF solution was directly heat-treated as it was, and then sodium carbonate and nonipol # 20 were added.
It was soaped with a hot aqueous solution containing 0 in small amounts, washed thoroughly with hot water and washed with water, and then dried.

By changing the types of resin processing agents and catalysts used and the heat treatment temperature as shown in Table 2, the resin adhesion rate on the work cloth
(%) Were compared. The results are shown in Table 2. The heat treatment time was 5 minutes.

From the results of Table 2, according to the present invention, an aprotic polar solvent (DMF) and a catalyst (TBA that promotes solid-liquid interface reaction).
B and DDAO), the adhesion rate of the resin processing agent to the fiber is remarkably excellent as compared with the case of using water as a solvent and the case of using a general metal catalyst as a catalyst. .

Example 3 A test cloth (palace crepe) was dipped in a DMSO solution containing 30% by weight of a resin finishing agent and 3% by weight of a catalyst to obtain about 90%.
After squeezing with the squeezing ratio of 100 ° C., 120 ° C., 140 ° C. for 5 minutes, and then sodium carbonate and nonipol # 2
It was soaped with a hot aqueous solution containing 00 in small amounts, washed thoroughly with hot water and washed with water, and then dried.

As a resin processing agent, elastron MF9 and the elastron MF9 are distilled under reduced pressure to remove alcohol,
The elastron MF9 modified product containing DMSO in an amount corresponding to the alcohol content removed thereafter was used to compare the resin adhesion rate (%) to the work cloth. The results are shown in Table 3.

From these results, it is confirmed that the effect of the catalyst in the present invention is confirmed and, at the same time, the solvent effect of DMSO is lowered due to the coexistence of the alcohol component as the protic solvent.

Example 4 Tolylene diisocyanate (30% by weight) and a catalyst (3% by weight) were added to DMSO as a resin finishing agent, and a test cloth (palace crepe) was immediately immersed in this solution and squeezed to about 90%, and then 100%. It heat-processed at 3 degreeC for 3 minutes. Then, it was soaped with a hot aqueous solution containing sodium carbonate and nonipol # 200 little by little, washed with hot water, washed with water, and then dried.

Table 4 shows the resin adhesion rate (%) of the product.

Since commercially available resins are stably stored as products for a long period (half a year to one year), some measures have been taken.

Most of the resins have components dissolved in alcohol (methanol, ethanol, propanol). And
This alcohol solution is used by dissolving it in water. Therefore,
When the product is used by dissolving it in DMSO instead of water, the working fluid contains some alcohol (more than usual). In Examples 1 to 3, the data is used in this form. By the way, since alcohol is the same protic solvent as water, it is considered that it reduces the solvent effect of DMSO, which is an aprotic solvent. In Example 4, the alcohol content was removed from the product by applying as little heat as possible by vacuum distillation, and the removed amount of DMS was used.
O was added, and the alcohol content in the working fluid was lowered by this operation. In Example 5, one component, tolylene diisocyanate itself, was dissolved in DMSO. Therefore, the alcohol content in the processing liquid is 0%.

However, as seen in Examples 3 and 4, the inclusion of a protic solvent in the working fluid reduces the solvent effect of the aprotic solvent. Therefore, even when other resins and other fibers are used, it is considered that even more excellent results than the results of Examples 1 to 3 can be obtained by removing the protic solvent (alcohols) from the processing liquid. To be

Example 5 An aqueous solution containing 30% by weight of a resin processing agent and 3% by weight of a corresponding catalyst and a DMSO solution containing 30% by weight of a resin processing agent and 3% by weight of catalyst DDAO were prepared, and a test cloth (Ichikoshi Chirimen) was prepared. ) Was dipped and squeezed to about 90%. Those soaked in the aqueous solution are dried at 80 ° C for 3 minutes and then heat treated, those soaked in the DMSO solution are heat treated as they are, and then soaped with a hot aqueous solution containing sodium carbonate and nonipol # 200 little by little and washed with hot water. After sufficiently washing with water, it was dried to prepare samples with a resin adhesion rate of 1%, 3% and 5%.

The heat treatment temperature was 120 to 140 ° C., and during the drying and heat treatment, the cloth was fixed to the width before processing with a pin tenter.

Next, a shrinkage rate test was performed on these samples. The results are shown in Table 5.

Further, in the conventional method, a method similar to the above has been proposed for the processing of methylolmelamine resin, which makes the texture hard. The results are shown in Table 6.

Since Ichikoshi Chirimen uses strong twist yarns as weft yarns, it shrinks greatly, and its shrinkage prevention technology has not been known until now.
However, when a catalyst that accelerates the solid-liquid interface reaction is used as the catalyst and an aprotic solvent is used as the solvent, a more excellent shrinkproofing effect than before can be obtained.

Further, in the conventional method, even when a methylolmelamine resin, which has a very hard texture, is used, relatively soft processing is possible.

Example 6 A test cloth (palace crepe) was dipped in a 1N DDAO aqueous solution, squeezed to about 90%, and then dried at 80 ° C. for 5 minutes. Then, it was immersed again in a DMSO solution containing 30% by weight of ethylene glycol diglycidyl ether as a resin processing agent, squeezed to about 90%, and then cured at 80 ° C.
Then, soaping with a hot aqueous solution containing a small amount of sodium carbonate and nonipol # 200, washing with hot water and washing thoroughly with water, and then drying, samples A1 and A with resin adhesion ratios of 1% and 5%, respectively.
2 were created respectively.

On the other hand, the palace crepe was immersed in a 1N KSCN aqueous solution, squeezed to about 90%, and then dried at 80 ° C. for 5 minutes.

Then, the resin processing agent was immersed again in an aqueous solution containing 30% by weight of ethylene glycol diglycidyl ether to obtain about 90%.
After squeezing, the mixture was cured at 90 ° C. Then, the samples were soaked with a hot aqueous solution containing sodium carbonate and nonipol # 200 little by little, washed thoroughly with hot water and washed with water, and then dried to prepare samples B1 and B2 having a resin adhesion rate of 1% and 5%, respectively.

Next, the yellowing degree (ΔY1) of the unprocessed cloth, A1, A2, B1 and B2 was determined at each irradiation time. The results are shown in FIG.

Epoxy resin processing is known to be excellent in the process of preventing yellowing of silk, but if a compound that accelerates the reaction at the solid-liquid interface is used as the catalyst and an aprotic polar solvent is used as the solvent, it is more excellent in preventing yellowing. It turns out that the effect is obtained.

EFFECTS OF THE INVENTION In the present invention, by using a quaternary ammonium salt or an amine oxide as a catalyst in the presence of an aprotic polar solvent, a resin-treating agent is quickly reacted with silk fiber, and its texture and The shrink resistance, yellowing resistance, chemical resistance and the like of the silk fiber product can be modified without adversely affecting the strength.

BRIEF DESCRIPTION OF THE DRAWINGS The drawings are graphs showing the effect of preventing yellowing when a silk fabric (palace crepe) is processed with a resin.

Claims (1)

[Claims] 1. A silk fiber product is impregnated with a resin processing agent reactive with silk fiber in an aprotic polar solvent in the presence of a quaternary ammonium salt or an amine oxide, and the solvent is volatilized. A method for processing a resin for a silk fiber product, which comprises performing a heat treatment under a condition that suppresses heat.