JPH11323735A - Modification of silk yarn - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modification process for silk yarn that can improve its functionality such as resistance to scratching or abrasion, to yellowing or browning, to washing and the like with a reduced amount of resin application without damage to fabric hand of the silk yarn. SOLUTION: The silk yarn is wound up around a perforated bobbin, as the yarn layers hold a large volume of spaces therein and dyed in a cheese- dyeing equipment, as the dyeing solution is circulated to carry out the scouring and the treatment with 0.1-5 normal aqueous solution of polyethylene glycol and the resin treatment. It is recommended that the treatment with the aqueous polyethylene glycol solution is followed by drainage and drying before the resin treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for modifying silk yarn using an epoxy resin.

[0002]

2. Description of the Related Art In general, silk fabrics are mainly made of woven fabrics in which raw silk is woven and then refined. However, as a recent trend in fashion, there is an increasing need for a pre-woven fabric style in which weaving is performed using a refined silk thread.
The characteristics of the hand are that it has a waist, a tension, a swelling without a core, and is excellent in sensation of dryness and dryness as compared with a post-knit fabric. However, removing sericin from raw silk by scouring and weaving in a state in which fibroin is exposed tends to cause threads and hits on the silk, and the luster and feeling peculiar to the silk tend to be impaired.

[0003] That is, a series of steps such as refining and dyeing of a silk thread are usually performed in the state of a skein yarn, and the work time of this series of steps requires a long time of 3 to 6 hours. When processing in a skein state by an over-meyer, a rotating back, or the like, the yarn is subjected to tension, and the surface of the yarn is liable to be fluffed, and satisfactory results are not always obtained in both productivity and quality. In addition, the efficiency of processes such as skein picking, skewing and rewinding before and after dyeing is poor, and manual work requiring skill is mainly performed, resulting in high cost.

[0004] Therefore, the silk has excellent feeling, luster, drapability, and the like, and has been widely used because of these characteristics. In order to solve this drawback, there has been an attempt to use an epoxy resin as a more durable modification method.

As a method for processing silk thread, there are immersion heating method, pad steam method, pad dry steam method, pad dry cure method and the like. For example, an aqueous solution of a processing agent (eg, using a skein dyeing machine) is used. If the resin is adsorbed on the fiber in the suspension or reacted, most of the resin useful for the adsorption or cross-linking reaction on the fiber is self-condensed in a few percent and deposited on the fiber surface to cure the fiber. This causes disadvantages such as worsening of feeling and lowering of strength. Therefore, such a method cannot respond to a request from apparel.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves such conventional disadvantages, has a small amount of resin adhered, does not impair the feeling of silk thread, has good dyeability, and has excellent thread and thread resistance. It is an object of the present invention to provide a method for modifying silk yarn that improves functionality such as yellowish browning and washing resistance.

[0007]

According to the present invention, a scouring process is performed while circulating a processing solution in a cheese dyeing apparatus in a state in which a silk thread is wound up with a hole bobbin having a lot of voids in a thread layer. The above problem was solved by performing treatment with a 0.1 to 5N aqueous solution of polyethylene glycol and processing with an epoxy resin.

According to the method of the present invention, several to a dozen or more raw yarns are plied or twisted, which are softened in advance on a bobbin with a soft winder, and the yarn layer is wound with as many voids as possible. Attached to a cheese dyeing device (a sealed device, in which the processing liquid circulates through the bobbin hole through the yarn layer, and the temperature inside the device can be arbitrarily controlled by a controller) I do.
In such an apparatus, continuous processing is possible by changing the treatment liquid circulated in the apparatus according to the purpose without moving the yarn wound on the bobbin at all.

[0009] The silk thread subjected to scouring to resin processing by such a method can be woven, knitted or dyed with high quality, and can be easily mixed with other fibers.

As will be described later in detail, after the treatment with the aqueous solution of polyethylene glycol, the silk thread is preferably wound up on a bobbin, dehydrated and dried, and then subjected to resin processing by circulation of an epoxy resin liquid.

Next, the method of the present invention will be described for each step. The silk treatment in the treatment liquid circulation system is preferably performed in a cheese dyeing apparatus. 1. Scouring method The scouring method is not particularly limited, and a usual silk kneading method can be used. Weak alkalis such as sodium silicate, sodium carbonate and sodium bicarbonate conventionally used in silk scouring, soaps, surfactants, reducing bleaching agents such as hydrosulfite, sequestering agents such as disodium ethylenediaminetetraacetate, etc. Using 9
It may be carried out by a method of completing scouring, that is, dissolving sericin at 5 to 130 ° C. over several tens of minutes to several hours,
In the treatment liquid circulation method of the present invention, enzymatic scouring which produces relatively little soap scum is appropriate. Enzymatic scouring is effective in preventing overscrutiny and kneading, and data management can be performed relatively easily. After scouring, it is preferable to repeatedly carry out washing by circulating hot water or the like (for example, washing is repeated twice at 60 ° C. × 10 minutes).

2. Polyethylene glycol aqueous solution treatment Polyethylene glycol (hereinafter referred to as PEG) has a molecular weight of 200 to 10,000, preferably 400 to 200.
0 may be used as a 0.05 to 5 normal (preferably 0.1 to 1 normal) aqueous solution, and the PEG aqueous solution is allowed to act while circulating through a silk thread in the apparatus, and is removed by ordinary water washing. It is possible to almost completely remove alkalis, surfactants and bleaching agents (about 1% of the weight of the yarn), which are impossible, as well as to swell the inside of the purified fibroin fiber and the amorphous region. The resin monomer used in the processing step can easily enter the inside of the fiber. After treatment with the aqueous PEG solution, i.e. after draining the aqueous solution, the silk thread remains wound on the bobbin to complete the removal of the desorbed impurities and excess PEG, while leaving the necessary PEG functional. It is good to dehydrate, dry and transfer to the next resin processing. The dehydration / drying step is preferably carried out outside the apparatus by using a silk centrifugal dehydrator for cheese or a microwave reduced-pressure drying apparatus, while the silk thread is wound on a bobbin.

[0013] In the case of raw silk, sericin is reduced to 20-
About 25% of the resin is dropped, and as a result, the initial shape wound on the bobbin is broken, which may result in subsequent resin processing or dyeing unevenness. In such a case, after drying, rewind with a winder and perform resin processing. And a dyeing step.

3. Resin processing method The following resin processing is a method in which a silk thread wound on a bobbin is mounted again in a processing liquid circulation type apparatus, and a processing liquid, that is, a resin processing liquid is circulated and acts on the silk thread. What is necessary is just to implement. This processing can be carried out in the same cheese dyeing apparatus as in the scouring and the PEG aqueous solution treatment. However, when a large amount of processing is continuously performed, the scouring, the PEG aqueous solution treatment, and the resin processing may be performed in different apparatuses. .

The resin processing may be carried out by circulating a commercially available epoxy resin aqueous solution (for example, a 0.1 to 50% aqueous solution) for resin processing in the apparatus. Is maintained at 60 to 140 [deg.] C. for 30 to 180 minutes, and the aqueous solution is sufficiently impregnated into the fiber to promote the reaction between the resin monomer and the fiber, the polymerization of the monomer, and the crosslinking reaction between the fiber and the resin. Note that the epoxy resin aqueous solution may contain a urethane resin or the like.

In the present invention, since all the steps from scouring to resin processing are performed in a state where the silk thread is wound on a bobbin, the silk thread is applied to the resin while maintaining the feeling, gloss, drape property and the like. Processing becomes possible, and moreover, resin processing can be performed more efficiently because PEG processing is performed before resin processing.

Usually, in the case of fiber processing using an epoxy resin, a pad dry cure method is used in which the resin is diluted with water, a low-boiling alcohol or the like and applied to the fibers, and the medium is removed at a low temperature. When the fiber is immersed in an aqueous epoxy resin solution, heated with a catalyst added, the epoxy resin polymer (generally hardly water-soluble) formed in the aqueous solution is deposited on the fiber surface and hardly detached even by washing. It has been considered difficult to perform fiber processing using an aqueous solution of an epoxy resin using a dyeing machine under the same conditions as those for dyeing a fiber, since the physical properties of the fiber are significantly reduced. However, in the present invention, the use of PEG under the conditions described above enables efficient resin processing.

In the present invention, a commercially available catalyst such as a neutral salt as a reaction catalyst for a resin monomer is used without using a reagent.
Pre-impregnated PEG promotes the reaction between the resin and the fiber inside the fiber, minimizing the polymerization reaction between the resins on the fiber surface seen in conventional resin processing and minimizing the generation of homopolymer .

The scouring residue such as an alkali agent hinders the reaction of the epoxy resin and causes a reaction unevenness, and the formation of a homopolymer impairs the original feeling of silk and causes the silk to become coarse and hard. By dissolving and removing the impurities inside the fiber by using PEG, and further by saturating the PEG, the reactive resin processing agent can be uniformly reacted (cross-linked or polymerized) even inside the fiber. Good feeling and a unique resin processing effect can be obtained.

According to the present invention, a bath ratio of 1: 1 is obtained by a "solution method" which is not the conventional resin processing (pad dry cure).
Resin processing becomes possible with an efficiency of about 10 or more. Also,
In the present invention, unlike the conventional resin processing, there is no deposition of the homopolymer of the resin used on the fiber surface, and the surface of the silk fibroin fiber itself shows the luster and luster of the silk, maintaining its beauty for a long time, and , Which eliminates the flaw of silk (fibrillation), which is a drawback of silk, and which is strong and does not fibrillate,
It is possible to obtain a beautiful silk thread excellent in color development even when dyed by a conventional method, and a silk thread excellent in fixing effect of sericin in which the amount of sericin dissolved and removed in the scouring step is adjusted to remain.

As the dyeing method, standard dyes such as acid dyes, direct dyes, basic dyes, gold-containing dyes, acid mordant dyes and reactive dyes commonly used for silk dyeing are used. It is dyed using the dyeing device as described above in the prescription. The dyed yarn is deeply dyed and is excellent in various fastnesses.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to Examples. In the Examples, "parts" and "%" indicate "parts by weight" and "% by weight" unless otherwise specified. In the examples, the silk thread (raw silk) is wound around a bobbin and processed. This winding step is an important step that greatly affects the subsequent scouring to dyeing results. In each example, about 600 g of silk thread was wound on a parallel bobbin having a diameter of 64 mm using an SSP-Precision winder manufactured by Kozu Seisakusho under the following conditions. Wind number 2.7700 Contact pressure 380-535 Initial tension 5.8-6.6

Example 1 A raw silk yarn of 400 t / m / 2 in 27 was wound up softly around a bobbin (tube) and loaded into a processing solution circulation type cheese dyeing apparatus, and the following treatment was carried out in the apparatus. Carried out. Refining treatment: 1 g / L of protease and nonionic surfactant 0.5 kept at 50-60 ° C from a stock tank
g / L of a mixed solution (scrumming solution) was injected, and circulated in the apparatus at 60 ° C. for 3 hours to dissolve and remove sericin in raw silk. Washing: After the scouring solution was discharged, washing with hot water at 50 to 60 ° C. for 10 minutes was repeated twice, and washing water was circulated in the apparatus to complete washing. PEG treatment: circulating a 0.2N aqueous solution of PEG-400 (polyethylene glycol having an average molecular weight of 400: manufactured by Daiichi Kogyo Seiyaku) to remove trace components remaining in raw silk;
After the inside of the fibroin fiber and the non-crystalline region were saturated with PEG, the PEG solution was discharged, and the scoured raw silk was dewatered while being wound on a bobbin, and then microwave-dried. Resin processing: 15 g of ethylene glycol diglycidyl ether (Epiol E-100: manufactured by Daiichi Kogyo Seiyaku)
The L solution was circulated in the apparatus at a bath ratio of 1:10 to sufficiently impregnate the fibers, and then the temperature inside the apparatus was raised from 40 ° C. while circulating the resin solution, and heated to 120 ° C. in 90 minutes. The reaction was terminated by heating, and the resin solution was discharged. Soaping: A nonionic soaping agent is injected from a stock tank, heated to 80 ° C., circulated in the apparatus for 15 minutes to perform soaping, and after discharging the soaping liquid, hot water washing and water washing are repeated. Finished processing. The steps (1) to (3) were carried out in the same cheese dyeing apparatus. However, in the dewatering / drying step, the raw silk wound on the bobbin was taken out of the cheese dyeing apparatus and centrifugally dehydrated for cheese at a rotation speed of 3500 rpm for 2 minutes. After dehydration, in a microwave vacuum drying apparatus, under a vacuum of 60 to 70 mmHg,
A method of drying at a power of 380 mA of microwaves for 40 minutes was performed.

Comparative Example 1 The same raw silk as in Example 1 was subjected to scouring only under the same conditions, washed with water, and then 15 g of ethylene glycol diglycidyl ether.
/ L, immersed in an aqueous solution containing 100 g / L of sodium sulfate as a catalyst and having a bath ratio of 1:10, and heated at 40 ° C.
Then, the temperature was raised to 120 ° C. for 90 minutes to terminate the reaction, and then the processing was completed by repeating soaping, hot water washing and water washing.

Comparative Example 2 The same method as in Comparative Example 1 was carried out except that sodium acetate 10 g / L was used instead of sodium sulfate 100 g / L.

A dyeing test and a thread test of a fabric woven using the silk yarns obtained in Example 1 and Comparative Examples 1 and 2 as warps and wefts were performed by the following methods. Table 1 shows the results. Dyeing test Each product was dyed by the following three dyeing methods, and the dyeing rate (K /
S) was measured and calculated by KURABO-COLOR7 (a measuring device of Kurashiki Spinning). (1) Dyeing with acid milling dye Dye (KM Blue GSL-ED, manufactured by Nippon Kayaku) 2% owf sodium sulfate 10% owf penetrant (funnel oil) Dyeing solution containing 2% owf at 90-100 ° C, bath Stained at a ratio of 1: 100. (2) Dyeing with metal-containing acid dye Dye (Irgalan Blue 3GL manufactured by Ciba-Geigy) 2% owf sodium sulfate 10% owf penetrant (Alazine D) A dye liquor containing 2% owf, at 90-100 ° C., bath ratio 1: Stained at 100. (3) Dyeing with reactive dye Dye (Lanasol Blue 3g, Ciba-Geigy) 3% owf Sodium sulfate (added in two portions) 2% solution Leveling agent (Textport) 0.2% solution Sodium carbonate 0.4% solution The dyeing | staining was carried out at 90-100 degreeC and the bath ratio of 1: 100.

Abrasion resistance test A test cloth was cut to a size of 2.2 cm × 22 cm long in the longitudinal direction and rubbed 300 times with a friction tester specified in JIS-L823 while moistening the sample with distilled water. did. The state of the test cloth after 300 times of rubbing was judged on a scale corresponding to the state of rubbing according to the number of times of rubbing of the unprocessed cloth, and the grade was shown as rubbing resistance. Grade unprocessed cloth friction number thread state 5th grade 30 times The thread can be slightly confirmed with the naked eye. Class 4 50 times 100th grade 3 thread. Class 2 200 times First grade 300 times.

Table 1 Dyeing ratio Sample resin adhesion amount (%) Acid dye- containing dye Reactive dye thread resistance Example 1 6.2 1.86 7.31 10.11 Grade 5 Comparative Example 1 8.2.1. 75 6.77 9.76 5th grade Comparative example 2 7.5 1.55 6.70 9.25 4th to 5th grade Raw cloth 0.0 0.75 4.77 8.76 1st grade

As shown in Table 1, the fabrics woven using the yarns processed in Example 1 and Comparative Examples 1 and 2 are all dyed darker than the unprocessed cloth, and The thread property was also good. In particular, the yarn using the yarn of Example 1 in accordance with the present invention is extremely superior to the comparative example in both the dyeing rate and the threading resistance, despite the small amount of the resin adhered. In addition, it was possible to obtain a product excellent in feeling and silk luster.

Next, the cloth woven from the yarn processed in Example 1 and the cloth woven from the unprocessed yarn were washed for 60 minutes in a home washing machine. Although the yarn breakage was remarkable and the appearance was very poor (see FIG. 1A), the fabric according to Example 1 according to the present invention had a uniform appearance, gloss and wind as before washing. Both were excellent (see FIG. 1B).

Example 2 A raw yarn plied and twisted according to the following formulation was wound into a bobbin with a soft winder and then softly loaded into an apparatus, scoured according to Example 1, treated with PEG-400, and wound on a bobbin. Dried. 25 g of ethylene glycol diglycidyl ether (SR-2EG: manufactured by Sakamoto Yakuhin Kogyo)
/ L and heat-reactive water-soluble urethane resin (Elastron C-
52: manufactured by Daiichi Kogyo Seiyaku) to prepare a mixed solution of 5 g / L,
After circulating in the apparatus and sufficiently impregnating the fibers, the temperature in the apparatus was raised to 120 ° C. according to Example 1 to complete the reaction, and the processing was completed by repeating soaping, hot water washing, and water washing, Stained with reactive dye. Twisted yarn Z 270T / M (S650T / M / 21D x 3 pieces x 3, S450T / M / 21D
X 3 pieces x 2)

Example 3 Using silk spinning (2/60), scouring was carried out according to Example 1.
After washing, a 0.5N aqueous solution of PEG-400 is circulated to remove trace components remaining in raw silk and to fill PEG into the inside of fibroin fiber and the non-crystalline region. After discharging, the scoured silk thread was dried while wound on a bobbin. Further, a 15 g / L solution of ethylene glycol diglycidyl ether (SR-2EG: manufactured by Sakamoto Yakuhin Kogyo) is circulated through the apparatus to sufficiently impregnate the fibers, and the temperature in the apparatus is reduced to 120 ° C. according to Example 1. The temperature was raised to complete the reaction. Next, a soaping liquid is poured from the stock tank, heated to 95 ° C., circulated in the apparatus for 15 minutes, soaped, and then repeatedly washed with hot water and water, and subsequently a dyeing solution of the reactive dye is introduced into the apparatus. The silk thread was dyed while wound on a bobbin.

Example 4 Using / 4 pieces of raw silk 21, scouring and threading resistance treatment were carried out in the same manner as in Example 1, followed by dyeing with an acidic gold-containing dye.

Example 5 The raw silk 31 was subjected to scouring and abrasion resistance treatment in accordance with Example 1 using / 2 of the raw silk 31, and then dyed with an acidic gold-containing dye.

The silk thread processed in Examples 2 to 5 was subjected to the dyeing test and the thread resistance test by the above-mentioned methods. Table 2 shows the results. Table 2 Dyeing rate Sample resin adhesion amount (%) Gold-containing dye Reactive dye thread-resistant untreated silk yarn 0.0 3.72 1.33 Class 1 Example 2 8.5 ─ 3.8 Class 5 〃 36 6 ─ 4.5 4-5 class 〃 4 5.3 7.2 ─ 4-5 class ５ 5 6.5 6.7 ５ 5 class

As can be seen from Table 2, the processed yarns according to the present invention are all dyed dark and have excellent thread resistance.

EXAMPLE 6 A half of raw silk 21 for warp and a quarter of raw silk 21 for weft were softly wound around a bobbin with a soft winder, and then loaded into an apparatus, and a 0.2N aqueous solution of PEG-400 was circulated. Processing was performed in the same manner as in Example 1 except that the sericin-fixed yarn was obtained. Further, the processed yarn was dyed with an acidic gold-containing dye while being wound on a bobbin. Obtained dyed yarn (sericin fixing yarn)
Was used to weave the hand-woven belt. In the band using unprocessed yarn, the occurrence of chalk marks, which is a major drawback of the raw dyeing band, is remarkable, but in the band using the yarn processed in this example, the occurrence of chalk marks is significantly reduced, and the quality is extremely high. It became good.

[0038]

According to the method of the present invention, it is possible to stably and uniformly process a resin, and it is possible to remarkably improve the thread resistance (prevention of fluffing) and the dyeing property with a small amount of resin adhered. Furthermore, while the yarn wound on the bobbin remains stationary, scouring, thread prevention, and dyeing can be performed consistently, and low-cost, high-quality modified silk yarn can be obtained.

[Brief description of the drawings]

FIG. 1 is an electron micrograph showing a surface state of a fabric after a washing test. A shows a fabric woven with unprocessed yarn, and B shows a fabric woven with a yarn processed in Example 1.

Claims (2)

[Claims] In a cheese dyeing apparatus, a silky yarn is wound up with a hole bobbin having a large amount of voids in a yarn layer, and while the treatment solution is circulated, a scouring treatment is performed. A method for modifying silk thread, comprising performing treatment with a prescribed aqueous solution and processing with an epoxy resin. 2. The method for modifying silk thread according to claim 1, wherein after the polyethylene glycol aqueous solution treatment, dehydration and drying are performed, followed by an epoxy resin processing treatment.