JPH05195431A - Method for processing to provide silk yarn product with function - Google Patents

Abstract

PURPOSE:To improve wear resistance, yellowing and browning denaturation, wrinkle resistance, etc., by immersing silk yarn in polyethylene glycol, drying, supplying the yarn with an aqueous reaction solution of a polyfunctional epoxy compound by making water content of the reaction solution in a specific range and subjecting the yarn to wet heat treatment with saturated steam occurring with hot air. CONSTITUTION:A product of silk yarn is impregnated with polyethylene glycol having phase transfer catalyst ability, dried and then supplied with an aqueous reaction solution of a glycidyl ether as a polyfunctional epoxy compound by making water content in the reaction solution 40-100wt.% based on the product of silk yarn. The silk yarn is put in a reaction chamber of a closed treating device, heated by sending hot air while rotating, and change of concentration and distribution of the epoxy compound is suppressed. The yarn is subjected to wet heat treatment with saturated steam produced from water contained in the yarn to extremely improve defects such as wear properties, yellowing and browning denaturation, wrinkle resistance and washing shrinkage without damaging excellent touch, handle, gloss, luster, etc., of characteristic silk yarn.

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 excellent functionality to a silk fiber product. More specifically, the present invention relates to a yarn, a knitted fabric comprising silk fiber as a main component,
While retaining the excellent sensory characteristics peculiar to silk fibers in fiber aggregates such as woven fabrics and sewn products, it has been pointed out that silk fibers have long been pointed out as abrasion, yellow browning, wrinkle resistance and washing shrinkage. The present invention relates to a processing method for imparting functionality that significantly improves the above.

[0002]

2. Description of the Related Art A modification process for imparting easy care to silk fiber products while maintaining the organoleptic properties derived from the excellent touch, texture, gloss and luster that silk fibers originally possess. Technology has been divided into three groups and developed. The first is the silk fiber, which has been developed, expanded, and rationalized, which is known as a processing method for imparting a heavy feel and unique luster to silk fiber products with tin and tannic acid. This is an intra-fiber polymerization method called grafting with vinyl monomers, which is mainly aimed at product price control. The second is a modification processing method under conditions modified by a thermosetting resin initial condensate applied to the processing of fibrous fiber products or a fibrin reaction type resin or a reaction agent. The third is a processing method so-called chemical processing, which is mainly intended to impart a crosslinking effect by a polyfunctional compound such as an epoxy compound.

However, the first processing method is intended for general apparel applications in which excellent consumption characteristics are to be realized while retaining the original sensory characteristics of silk fibers, so that the purpose can be easily analogized. From the viewpoint of imparting the functionality required for, there are areas that deviate significantly. In the second method, microscopically, the resin composition formed inside the fiber is roughly cured, and the silk fiber itself is reduced in texture and yellow due to high temperature heat treatment under dry and wet conditions adopted during the processing step. In addition to the tendency to change, the improvement of wrinkle resistance does not always have the expected effect due to the entanglement of macroscopically declining sublimation of silk filaments whose freedom is restrained within the fabric structure. It has been pointed out.

As a countermeasure for these problems, a combination of urethane oligomers and the like has been proposed (JP-A-64-45).
No. 871), the problem of free formaldehyde, which is mentioned as one of the biggest difficulties in general apparel applications, is potentially included even in consideration of heat treatment conditions that allow it, and it is not possible to eliminate the drawback. Extremely difficult.

Therefore, the modification process for imparting desired functional characteristics to the silk fiber product while retaining the original sensory characteristics is focused on the third method. Actually, as a typical example, a modification processing method by a two-phase method (Japanese Patent Publication No. 52-38131) in which silk fiber saturated with an aqueous solution of a neutral salt is heated in an organic solvent solution containing an epoxy compound is a closed system. Specialized process (Tokuhei 2-5
It is a well known fact that it was commercialized by the development of Japanese Patent No. 3544), supplied to the market as washable silk, and widely established.

However, even these excellent production methods cannot promote reduction of processing time due to the two-phase method during the mass production process, which is pointed out as a difficulty in productivity.
Further, a problem has been extracted that the chlorine-based solvent used as the epoxy compound solution recommended for flame retardancy flows out of the system system with a small amount due to washing with water after completion of the reaction.

The inventors of the present invention, as a method for solving these drawbacks in the mass production state, first of all, to promote the reaction of the silk fiber and the epoxy compound with a polar aprotic solvent system, can improve the reaction rate. Found to be effective in promoting,
A technique has been established to significantly rationalize productivity by combining with heat treatment in high temperature steam (Japanese Patent Publication No. 2-42943). Furthermore, after pad-drying the phase transfer catalyst,
A method has been established in which an epoxy-containing polar proton solvent is padded and heated at atmospheric pressure, high pressure or high temperature without drying (Japanese Patent Application No. 3-167418).

However, in the process of mass production of the method, the following problems were highlighted. Polyethylene glycol is the most stable and safe for handling up to the next step of treating a silk fiber product impregnated with a phase transfer catalyst and drying with a polyfunctional epoxy compound aqueous reaction solution. , Relatively low price compared to other drugs.

Regarding a polyfunctional epoxy compound, when a polar protic solvent solution other than water is used, the viscosity of the epoxide solution increases, and it is necessary to control the satiety of silk fiber products by depressurizing or pressurizing the liquid. Becomes extremely difficult in the business, and the satiety work or its environment is significantly deteriorated.

However, when the most commercially advantageous aqueous solution of epoxide was adopted, the crosslinking reaction promoted by steaming treatment was expected in view of its weight change, as compared with the case of using other polar protic solvent solutions. There are some cases where the standard is not reached.

Further, when an epoxide aqueous solution is used, in comparison with continuous high-temperature steaming, batch-type atmospheric pressure or high-pressure steamed silk fiber products may generate reaction spots that are considered to be caused by steam spots. It was inferred from the stain spots after the treatment, and it was confirmed that the improvement was quite difficult.

[0012] Therefore, it is desired to promote the reaction by the continuous high temperature steaming method, but this method has a high production capacity, and energy cost is high for processing a large number of small lots of silk fiber products. I can't say.
Furthermore, contacting the silk fiber product with high temperature steam of 100 ° C. is not recommended from the viewpoint of deterioration in feeling.

As a typical example of a heating method for accelerating a reaction between a general silk fiber and an epoxy compound, a silk fiber product saturated with an aqueous solution of an epoxide is batched up into a conventionally known porous beam to form a film. The method of sealing and heating with such as does not lead to the elimination of reaction spots, but rather the problem that the distortion of the fiber assembly due to the shrinkage of the silk fibers that occurs during heating is fixed as wrinkles, etc. can not be corrected. Was extracted.

[0014]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made a modification process which is a process very suitable for on-site work, in which a polyethylene fiber glycol-impregnated and dried silk fiber product is filled with a polyfunctional epoxy compound aqueous solution. About technology,
As a result of diligent research on heating conditions for promoting the effective crosslinking reaction, in the reaction system, in the conventional steaming method in which steam of a specific temperature is passed from the outside, the fibers are saturated by the saturated steam in contact with the fibers. It was confirmed that the polyethylene glycol and the epoxy compound having the phase transfer catalytic ability contained therein induce fluctuations in the concentration or distribution on the fiber, resulting in the achievement of the expected crosslinking reaction rate being hindered. At the same time, it has been found that it is difficult to completely suppress the generation of steam contact spots on the fiber aggregate in association with the reaction spots.

The technical problem of the present invention is to suppress the concentration and distribution change of polyethylene glycol as a readily soluble phase transfer catalyst and epoxy compound evenly distributed on these silk fibers during the heating process as much as possible. ,
While maintaining the organoleptic properties derived from the appearance such as excellent feel / feel and gloss / gloss in the fiber assembly containing silk fiber as the main component, the abrasion property which has been conventionally pointed out as a defect of silk fiber, It is an object of the present invention to provide a technique for imparting functionality for significantly improving yellow browning, wrinkle resistance, washing shrinkage, and the like.

[0016]

In order to solve the above problems, the method for imparting functionality to a silk fiber product according to the present invention comprises:
A polyethylene fiber-impregnated and dried silk fiber product was filled with a polyfunctional epoxy compound aqueous reaction solution such that the water content in the reaction solution was 40 to 100% by weight based on the silk fiber product. After that, the treatment liquid-containing silk fiber product is heated by blowing hot air into the reaction chamber of the closed system treatment device, and wet-heat treated by saturated steam generated by the moisture contained in the silk fiber product. It is what

More specifically, in the processing method of the present invention, silk fiber products such as yarns, knits, woven fabrics and sewn products which are mainly composed of silk fibers,
In order to minimize the concentration and distribution changes of polyethylene glycol and polyfunctional epoxy compounds as a readily soluble phase transfer catalyst evenly distributed on silk fiber, it can be adjusted up and down in a closed reaction chamber, for example. The silk fiber product containing the polyethylene glycol and the epoxy compound is suspended and supported between the drive rolls thus arranged, and while the drive roll is slowly rotated, hot air having a required temperature is introduced and circulated. As a result, the temperature of the polyethylene glycol and epoxy compound aqueous solution contained in the fiber is gradually raised to accelerate the reaction. Therefore, since the reaction is carried out in saturated steam at a predetermined temperature under stable and mild conditions, compared with the drying or steaming heat treatment in the proposed method, while maintaining the organoleptic characteristics peculiar to silk fiber, It is possible to impart extremely excellent functional characteristics.

The promotion of the crosslinking reaction according to the present invention is microscopically required to be carried out on silk fibers containing a certain amount of water, and macroscopically, it is a fiber assembly to be modified. It is desirable to suppress the distortion caused by the processing to the maximum. Therefore, the volume ratio between the silk fiber product to be treated and the closed reaction chamber directly affects its modifying effect. Generally, the apparent specific gravity of the fiber product is unavoidably different depending on the form of the fiber aggregate, but the volume ratio of the silk fiber product and the reaction chamber to which the processing method of the present invention is applied is 20 times to 100 times. Double range is effective.

If the volume ratio exceeds 100 times, along with the increase in energy cost, there is a tendency that the improvement in wet wrinkle resistance is diminished due to the decrease in the water content in the fiber during the wet heat treatment. On the other hand, when it is 20 times or less, the strain generated in the fiber assembly being treated is fixed, and the quality of the fiber product tends to be remarkably lowered. Therefore, it is 20 to 50 times for fiber and yarn treatment, and 5 for fabric or sewn products.
The range of 0 to 100 times is preferable.

As the wet heat conditions used in the method of the present invention, generally, a treatment time of 1 to 3 hours can be adopted in a temperature range of 50 ° C. to 120 ° C., but a treatment of about 70 ° C. for 2 hours. Conditions are preferred.

The phase transfer catalyst has a molecular weight of 200-200.
Using 400,000 polyethylene glycol, an aqueous solution having a concentration of 0.01 to 2 is used to saturate the silk fiber product and dried. Since the silk fiber product containing the catalyst has a hygroscopic property, it is important to sufficiently control the storage before the epoxy compound is applied. Further, as the polyfunctional epoxy compound, for example, glycerin diglycidyl ether, ethylene glycol diglycidyl ether, glycerin triglycidyl ether, phenyl diglycidyl ether,
Examples thereof include diglycidyl ethers such as 1,4-butanediol diglycidyl ether.

FIG. 1 shows an outline of a closed system treatment apparatus equipped with a reaction chamber used for wet heat treatment of silk fiber with saturated steam when the method of the present invention is carried out. This closed system treatment apparatus is provided with a reaction chamber in which polyethylene glycol-impregnated and dried silk fiber product is filled with an aqueous reaction solution of a polyfunctional epoxy compound and then wrapped around a winding frame. In this reaction chamber, the circulating air volume can be adjusted so that the temperature distribution inside is uniform. Inside the reaction chamber, drive rolls are arranged corresponding to the upper and lower sides, and silk fiber products are placed on these rolls. Is suspended and heated while moving the product by rotating the roll to accelerate the reaction between the silk fiber and the epoxy compound in the saturated vapor from the moisture contained in the fiber.

Therefore, although not shown, in addition to the closed system treatment device shown in FIG. 1, a dipping tank for preliminarily impregnating the silk fiber product to be processed with polyethylene glycol, and the silk fiber product after the dipping A dewatering device such as a vacuum dehydrator for dewatering, a drying device for drying after the dewatering, a dipping tank for filling an aqueous reaction liquid of a polyfunctional epoxy compound, and the like are separately provided.

In the reaction chamber which can be closed in the closed processing apparatus, there is a heating facility for heating the silk fiber in the reaction tank, and water is injected from the lower part of the reaction chamber by the pump P to stop the reaction due to the heating. The water supply / drainage equipment for discharging and the solvent recovery equipment are connected by piping so that the organic solvent components etc. discharged by the solvent recovery equipment can be separated and removed, the working environment is improved, and the atmosphere or drainage is polluted by the solvent constituents. Is trying to prevent.

That is, in the reaction chamber, as a heating facility, a heating device for controlling the supply of the heating fluid by a valve SV is attached, and a circulation system passage equipped with a heater for supplying hot air into the reaction chamber. Is provided. Usually, the heating device is controlled so that the supply of the heating fluid by the valve SV is stopped after the silk fiber in the reaction tank reaches a certain temperature. On the other hand, the circulation system path is equipped with a fan with an inverter, a cooler condenser, a three-way valve V, and a heater for heating the circulating air with a heating fluid whose supply is controlled by a temperature control needle valve N.

On the other hand, the solvent recovery equipment is the three-way valve V
An activated carbon recovery device for introducing air exhausted from the device, a water separator for removing the water separated and recovered from the recovery device,
In addition, a drainage treatment device is provided, and the drainage from this drainage treatment device is discharged to the outside together with the drainage from the cooling water tank in the water supply and drainage facility. On the other hand, the exhaust gas released to the atmosphere by switching the three-way valve is exhausted to the outside through an activated carbon recovery device in order to adsorb and recover organic solvent components and the like.

[0027]

EXAMPLES Next, examples of the processing method of the present invention will be described. Example 1 A Japanese-style long-solden sword cloth (3/1 torn slanted pattern) fabric using two flat warp yarns, two flat yarns in the raw yarn 27, and four weft yarns in the raw yarn 27, was scoured, bleached, and dried by a conventional method. After finishing the finishing, the material is polyethylene glycol (molecular weight 4
00) of 0.5N aqueous solution was impregnated, squeezed to a squeezing ratio of 100% with a vacuum dehydrator, and dried with a short loop dryer. Then, it was immersed in an aqueous solution of a polyfunctional epoxy compound (EP-E100 manufactured by NOF Corporation, 10%), and wound up on a winding frame while squeezing to a drawing rate of 100% with a vacuum dehydrator.

The obtained fabric was removed from the winding frame and wound on a roller in the reaction chamber, and the fabric temperature in the reaction chamber was changed from room temperature to 75 while rotating the fabric at a constant speed (5 minutes-10 cm).
The temperature is raised to ℃ over 1 hour and the steaming temperature of 75 ℃ is adjusted to 1
After maintaining the temperature for 1 hour and further raising the temperature to 80 ° C. and maintaining the temperature for 1 hour, water was injected from the lower part of the reaction chamber to stop the reaction. After leaving it for 20 minutes, drain the water and take out the fabric, and soap it for 1 hour and 30 minutes by a conventional method to remove unreacted resin, catalyst, etc., then wash it with water and dry it with a hanging dryer to finish the Nolan run hole. I went.

The treated fabric thus obtained contained 7.8% by weight of the reaction product in view of the change in weight before and after the treatment, and the treated fabric was superior to the untreated fabric in the same or better level. In addition to the texture, appearance and feel, shrink resistance, yellowing resistance, wrinkle resistance (dry and wet wrinkle resistance), dyeing resistance, scratch resistance, washing resistance, etc. were remarkably improved. In particular, the texture was better than that of the cloth containing the reaction product at almost the same level, which was obtained by dry heat treatment in the same reaction system, and exhibited excellent wash and wear properties.

Example 2 According to the same manner as in Example 1, the temperature of the dough in the reaction chamber was changed according to Example 1 by using three warp raw yarns, three medium flat yarns, and ten weft yarns, twenty twists (left, right). As in Example 1, except maintaining the steaming temperature at 75 ° C. for 1 hour 30 minutes,
A treated fabric containing 5.8% by weight of reaction product was obtained.
The texture of the treated fabric was more flexible than that of the untreated fabric, and the same improvements as in Example 1 were observed in dimensional stability, scratch resistance, dyeability, and especially in color developability.

Example 3 While the raw silk 31 was being formed, it was impregnated with a 0.7N aqueous solution of polyethylene glycol (molecular weight 400), squeezed to a squeezing ratio of 60% with a centrifugal dehydrator, and dried at room temperature of 60%.
After drying at 0 ° C for 10 hours, it was immersed in an aqueous solution of a polyfunctional epoxy compound (EP-G100, 15% by NOF CORPORATION), squeezed to a squeezing ratio of 60% with a centrifugal dehydrator, and framed on the roller as it was. While rotating the thread at a constant speed (5 minutes-6 cm), the temperature of the thread in the reaction chamber is from room temperature to 70 ° C.
After raising the temperature over a period of time and steaming at 70 ° C for 2 hours, turn off the steam of the heat source and the closing temperature air flow rate adjustment switch, and
It was taken out after leaving the reaction chamber closed for an hour.

After that, soaping was carried out for 1 hour and 30 minutes by a conventional method to remove unreacted resin, catalyst, etc., and washing with water.
The treated yarn obtained by drying at 60 ° C. for 10 hours in a drying room is
From the weight change before and after the treatment, the reaction product contained 8.2% by weight. Weaving organge fabric with this treated yarn,
Even after scouring and bleaching by a conventional method, there is no reduction in kneading as shown in FIG. 2, and in the conventional organdy fabric, sericin fixation is insufficient, so that scouring and bleaching after weaving cannot be performed, including stain removal attached during weaving. However, the problem was solved and a practical sericin fixing yarn could be obtained. Further, the dyeing resistance and the abrasion resistance were also significantly improved.

Example 4 Six weakly twisted plied yarns of 35 mulberry yarns 35 were taken in the shape of a plaque, enzymatically scoured, bleached and dried by a conventional method, and then dry-cleaned in perchloroethylene at 70 ° C. for 1 hour. The treatment is carried out to remove the residual raw materials, colloids and oil-soluble components contained therein, followed by drying, and the washed yarn is maintained at the steaming temperature of 75 ° C. for 2 hours in accordance with Example 1, except that Example 1
Similarly to the above, a treated yarn containing 4.8% by weight of a reaction product was obtained.

As for the texture of the silk thread, the Young's modulus of the silk thread is 350 to 400 kg compared to 600 to 700 kg / mm of the raw silk.
/ Mm, softer and more flexible than filament yarn, and has an elongation of 29-31% compared to 19-21% of raw yarn.
Yes, it became a filament yarn with stretch. The strength is 3.6 to 3.9 g compared to 3.4 to 3.7 g / d of raw silk.
/ D. It is a weakly twisted yarn with stretch and has elastic properties (elastic recovery). In addition, the effect is particularly seen on the loudness (fluffing), and the touch has a soft sensation that has never been obtained. In addition, the cut surface has a standard shape, and the angle of reflection of light received by the yarn is different, resulting in a new luster that cannot be seen in raw silk.

Regarding the dyeability, as shown in Table 1, improvement in wet friction, which was not seen in the past, was observed. It was found that the drying after dyeing is preferably low temperature drying, and most preferably hygroscopic drying. In addition, a remarkable effect was confirmed in improving the devitrification phenomenon and the like, and it is expected to have a wide range of development in addition to knitted fabrics.

[0036]

Example 5 Two pieces of raw yarn 31 in raw yarn 31 for warp, and dry twisted yarn in raw yarn 31 for weft 6
A five-ply satin shaving machine for kimono waving composed of these yarns was scoured, bleached and dried by a conventional method, and then the same procedure as in Example 2 was followed.
A treated fabric containing 7.2% by weight of reactive products was obtained in the same manner as in. As the effect, the same effect as in Example 1.2 was observed, and in particular, the wrinkle resistance was improved as shown in FIG. 3 irrespective of the weak twist yarn woven fabric, and it was comparable to the untwisted plain twisted crepe of the strong twist yarn. It was found that the wrinkle prevention rate was improved. It is necessary to pay particular attention to avoid wrinkles in the work of winding on the frame while squeezing with a vacuum dehydrator in the resin attaching step. If the reaction is carried out with wrinkles, it cannot be suppressed once the wrinkles are reached, even in the soaping finishing step and the dyeing finishing step. Further, when wrinkles are positively applied to the weak twisted yarn woven fabric and an epoxy compound reaction liquid is applied to accelerate the crosslinking reaction, wrinkle processing excellent in washing resistance can be performed.

[0038]

According to the method of the present invention described above,
Concentration and distribution of polyethylene glycol as a readily soluble phase transfer catalyst and an epoxy compound evenly distributed in a fiber aggregate such as yarn, knitted fabric, woven fabric and sewn product composed mainly of silk fiber in the heating process It has been pointed out as a drawback of silk fibers while suppressing the change as much as possible, thereby maintaining the organoleptic properties derived from the excellent feel, texture, luster, luster, etc. originally possessed by silk fibers. It is possible to significantly improve abrasion resistance, yellowing resistance, wet wrinkle resistance, and the like, and at the same time, improve post-processing performance such as excellent dyeability and antistatic effect.

In addition, in the processing process, the crosslinking reaction is carried out in a highly safe aqueous system under extremely mild processing conditions, so that damage to other coexisting fibers or accessories can be significantly reduced. At the same time, it is possible to reduce many occupational safety and health and environmental conservation measures generally required for special processing.

[Brief description of drawings]

FIG. 1 is a block diagram showing an embodiment of an apparatus used for carrying out the method of the present invention.

FIG. 2 is a graph showing the sericin fixing test results for the treated yarn processed by the method of the present invention.

FIG. 3 is a graph showing the experimental results for the wrinkle-proof test results of the weakly twisted yarn fabric processed by the method of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaharu Masuda 1545-1 Oki, Sumiyako, Omiya-cho, Fuchu-gun, Kyoto (72) Inventor Toshihiko Masuda 40, Sugitani, Mineyama-cho, Fuchu-gun, Kyoto Masumi Stock Company Within

Claims (1)

[Claims] 1. A polyethylene fiber-impregnated and dried silk fiber product is mixed with a polyfunctional epoxy compound aqueous reaction liquid, and the water content of the reaction liquid is 40 to 100 with respect to the silk fiber product.
After being filled up so as to be contained in the range of wt%, the treatment liquid-containing silk fiber product was heated by blowing hot air into the reaction chamber of the closed system treatment device so as to be contained in the silk fiber product. A method for imparting functionality to a silk fiber product, which comprises subjecting a moist heat treatment to saturated steam generated by moisture.