JP4422087B2 - Method for dyeing silkworms, method for producing dyed raw silk, dyed silk knitted fabric - Google Patents

Description

  The present invention relates to a method for dyeing fibroin protein without heating the cocoon, a method for producing colored cocoons and raw silk dyed by the method, and a dyed silk knitted fabric.

The dyes for dyeing silkworms and raw silk are roughly classified into indigo, quinone, triphenylmethane, phthalocyanine, and azo, and all pigments were mainly fixed by heat treatment. In these methods, in the case of silkworms and raw silk, sericin protein is mainly dyed, and when dyeing is performed, most pigment dyes are peeled off together with sericin protein by scouring.
Based on these phenomena, post-dyeing has been carried out in the order of twisted yarn, scouring, dyeing and knitting since ancient times. In addition, the method of scouring (post-kneading) and dyeing after weaving like a chirimen / raw fabric has been impossible to express with complex colors and multiple colors. Also, heat treatment by scouring and dyeing may cause folds and wrinkles in the fabric, greatly impairing the original gloss and texture of raw silk.

Therefore, a method for producing colored raw silk by applying a dyeing material on the back of the mature koji and reeling the koji colored in the same color as the dyeing material made by the mature koji is used as raw silk (Patent Document 1). reference). In addition, as a method for producing a woven or knitted fabric using pre-dyed silk raw silk, sericin covering the silk raw silk and internal fibroin are dyed in the same color, and the dyed raw silk is woven or knitted, and then sericin is enzyme There is also known a method of decomposing by (see Patent Document 2). However, regarding the dyeing described in these documents, there is no description as to what kind of dye is used, and it is considered that dyeing is performed using a conventionally used dye.
JP 2000-333555 A International Publication No. WO97 / 31147

  It seems that color expression that emphasizes eclectic color and hue by twisting different dyed yarns seems to be performed in part, but in the case of raw yarn, there is almost no work of expressing different colors by combining the colored yarns. For natural fibers such as wool and cotton, and chemical fibers such as polyester and acrylic, those that are dyed in multiple colors such as warp and rainbow yarn, film yarn such as lame yarn, gold and silver yarn, etc. There is something that targets quality change. Some silk yarns have been used as changing yarns such as lame covering yarn and silk thread. When the above-described color expression is attempted by dyeing raw yarn and twisting, raw dyeing is heated in the dyeing process. For this reason, twisting is required to avoid sticking. Even in view of these processes, conventionally, a single yarn having a minimum fineness of 21 to 27d is required, and even if dyeing can be performed, the colors are not assimilated in the process of combining the colored threads, and there is a deep color or iridescence. The effect did not occur. In addition, color spots are generated depending on the number of times of twisting, and it is impossible to maintain a stable and complex color. Therefore, the development of new products that have the original texture and gloss as raw material characteristics is expected.

  In view of the above-mentioned points, the present invention dyes fibroin protein, which is the central part of the yarn with a dye dissolved in a solvent, to obtain colored raw yarn by dyeing before scouring. The purpose is to obtain raw silk, silk and silk products of colors and textures that could not exist in the past. In addition, the present invention is an environmentally friendly dyeing method that does not use a mordant such as heavy metal during dyeing.

The present invention relates to dyeing cocoons characterized by immersing cocoons in a solution in which an azo dye or phthalocyanine dye, which is an oil-soluble dye, is dissolved in an organic solvent, and dyeing fibroin protein in the center of the cocoon thread Is the method. The dyed cocoons can then be boiled and reeled into raw silk. A plurality of silkworms dyed in different colors dyed with various dyes can be boiled at the same time and reeled to obtain raw yarns with multicolored complex tones to obtain various textile products with complex tones. it can. Furthermore, it is possible to obtain a raw silk leaving sericin in the boiled rice cake after dyeing.

  When the cocoon is soaked in a solution obtained by dissolving an oil-soluble dye in an organic solvent, the dye passes through the sericin protein and stains only the fibroin protein. Dyeing is robust, there is no color fading in boiled rice cakes, and if the raw silk leaves sericin by spinning the dyed silkworm, it is possible to feed out colored silk with a sense of elasticity. Moreover, since only fibroin protein is dyed, complex colored raw silk that cannot be expressed by dyeing can be produced by mixing and spinning dyed silkworms. In addition, the raw silk obtained by spinning the dyed cocoon is a raw silk having the original gloss and texture because the heat treatment step by dyeing is omitted.

  The cocoon used in the present invention may be either a rabbit or a wild cocoon, and dyeing can be performed not only in the state of cocoon but also in raw silk by spinning. By performing, the raw silk of the quality which was not obtained conventionally and which is mentioned later is obtained. In the present invention, dyeing is performed using a solution obtained by diluting an oil-soluble dye with an organic solvent. Examples of the colorant include acidic dyes, basic dyes, and pigments, and the dye is preferably an oil-soluble dye. As the oil-soluble dye, an azo dye or a phthalocyanine dye is suitable. Examples of the azo / phthalocyanine dyes include the registered trademark “VALIFAST COLORS” manufactured by Orient Chemical Co., Ltd., and commercially available oil-based marker inks may also be used as the oil-soluble dyes of the present invention. Can do.

In the present invention, the oil-soluble dye is diluted with an organic solvent. As the organic solvent, a mixed solution of toluene, methanol, and ethyl acetate, or a mixed solution of acetone, ethyl acetate, butyl acetate, castor oil, butanol, and the like is used. be able to. The mixed solution of toluene, methanol, and ethyl acetate is preferably used as a solvent mixed at a ratio of 55:25:20, but the mixing ratio is not limited to this range. A commercially available light removing solution can also be used as the solvent of the present invention. The thinner has a component similar to that of the light removal solution, but is not preferable since pigment precipitation is observed. In the dyeing step, an oil-soluble dye is dissolved in a solvent, diluted with a solvent to a predetermined color, prepared, and the soot is immersed in the solution. In dyeing, since the solution penetrates into the cocoon layer, the dye penetrates into the inside of the cocoon layer by instant immersion and dyes the central part of the cocoon thread . The dyed cocoon is used for reeling after air drying.

As the boiled rice bran method, pot cooking is performed as a colored koji method, but it is preferable to immerse the koji in water as a pre-boiled koji and then pull it up and soak in warm water, and re- immerse it in water. By this step, water can be absorbed in the basket. Water absorption is an effective pretreatment for feeding a large amount of yarn and eliminating the boiled layer. The color to be reeled is determined, and a color kite is prepared in consideration of the raw silk requirement. The boiled rice cake can be processed simultaneously with shaded color koji and a plurality of koji dyed in different colors. Put the salmon in hot water above 90 ° C, cover and boil, stop the heat and steam. Next, take the clues from all the kites and move them to the kites. If a small amount of boiled rice cake, a plurality of rice cakes dyed in different colors are cooked at the same time. In the present invention, since only fibroin protein is stained, the color does not transfer even if different color potatoes are cooked at the same time. When the amount of rice cake is large, it is efficient to cook the rice cake by color.

  For reeling, the number of grains to be raised is determined according to the target color and fineness of the kite from which the thread is drawn out, put in the rewinding pan, and the thread is aligned. Wind it on a frame. The role of the conjugation device in the color reeling is large, and it relates to the adjustment of the number of yarn twists and the stability of the color of the raw silk. In particular, in the case of heterogeneous color mixing, twisting and conjugation with a drum is more effective than a Kennel conjugation device in order to produce a stable color and iridescent effect. During spinning, in order to stabilize the fineness and color, if the oak or thin skin wrinkles appear, the wrinkles of that color are joined. The raw silk is a deep shade that cannot be expressed by koji dyeing or post-dyeing by reeling together with different colored wrinkles. In addition, the dye that has passed through sericin and fixed to fibroin is coated with sericin, and becomes moist and glossy raw silk.

  The color raw silk according to the present invention obtained as described above is characterized in that it has a natural silkiness and a hue that cannot be expressed by ordinary dyeing. The color raw yarn of the present invention can be made into a woven product using a conventional loom or knitting machine. Differences between the raw silk according to the present invention and the conventional dyed twisted yarn will be described below.

  Traditionally, as a process of handling raw silk, scouring is always performed as a pre-dyeing process, and sericin has been dropped to make it easier to dye the thread, creating the unique softness of silk. Currently, the use of silk has been diversified, and techniques such as strong twisted yarn and sericin fixing have been developed in order to give the material a sense of sharpness in the Western clothing, especially the knit industry. In the current dyeing process, dye fixing by heat treatment is performed. By the heat treatment for refining and dyeing, the raw silk has greatly changed its taste. In the present invention, dyeing is performed before scouring, so that sericin is left in a hard texture according to the use, or a plurality of wrinkles dyed in different colors are boiled at the same time and then simultaneously wound to obtain complex colors. It is possible to obtain a product that can be used in various directions, such as a soft thin silk fabric having Further, the raw silk dyed according to the present invention is excellent in fastness and has no fear of fading or discoloration due to temperature, so that the raw silk can be stably wound. The dyed raw silk of the present invention can be knitted and knitted in the same manner as ordinary raw silk, and can be widely used from thin materials such as chiffon and organdy to silk products having a hard hand. In the present invention, since it is dyed before scouring, it is effective when applied to Haedae, Shiose, crepe and the like that are scoured and dyed after weaving.

  Examples are shown below, but the present invention is not limited to these ranges.

Ingredients used in the dyeing process: 1kg (Gumma 200) 1kg (1,000 dried rice cakes)
Dye Red high fastness oil-soluble dye (trade name: VALIFAST RED
2303, Orient Chemical Industry Co., Ltd.) 10g
Solvent Toluene 550ml
Methanol 250ml Mixture 1000ml
200 ml of ethyl acetate
Put the dye and solvent in this order in a wide-mouth glass bottle, and adjust the solution to the target color. Dyeing penetrates into the cocoon layer by instant soaking because it penetrates the cocoon layer well. After dyeing, air-dry and use for reeling. A sample 1 is a cocoon before scouring in which the resulting red fibroin protein is stained.
A blue high fastness oil-soluble dye (trade name: VALIFAST BLUE 1603, manufactured by Orient Chemical Industry Co., Ltd.) was used as the dye, and dyeing treatment was performed under the same conditions as above to obtain a blue color dyed blue. (Sample 2)
Furthermore, a pale pink high-fastness oil-soluble dye (trade name: VALIFAST PINNK 2310, manufactured by Orient Chemical Industry Co., Ltd.) was used as a dye, and the same treatment as described above was performed to obtain a pale pink dyed color. (Sample 3)

Boiled rice cake method: Colored rice cake method (Nabei rice cake)
A color to be reeled is determined, and based on a color sample and a color scheme, a color kit made up of Sample 1, Sample 2, and Sample 3 is prepared in consideration of the necessary amount of raw silk. In this case, shades of shade and a plurality of shades dyed in different colors can be simultaneously processed by the following method.
(1) Boiled rice pre-treatment (water absorption)
Put the prepared jar in a water-absorbing jar (with lid) and immerse it in water for about 20 seconds. After pulling up, immerse in warm water of 70-80 ° C for 15 seconds. Immediately soak in water for about 20 seconds. By this step, water can be absorbed in the basket. Water absorption is a pretreatment necessary for feeding a large amount of yarn (eliminating boiled spots in the cocoon layer).

(2) Boiled rice cake Put the rice cake in hot water at 90 ° C or higher, cover and boil for 1 minute. Turn off the heat and steam for 3 minutes. Next, take the thread with a sorghum spear, take out the clues from all the spears, and transfer them to the spear. To prevent overboiled rice cakes, the boiled rice cakes and steaming time should be accurate.
If a small amount of boiled rice cake, a plurality of rice cakes dyed in different colors are cooked at the same time. Since only fibroin protein is stained, even if different color potatoes are cooked at the same time, the color will not transfer. When the amount of rice cake is large, it is efficient to cook the rice cake by color. In the boiled rice bran method of the present invention, a koji with extremely poor unwinding can be wound by adjusting the cooking time and the steaming time.

(3) Spinning method Determine the number of grains to be raised according to the target color and fineness of the spear from the threadhead, put it in a revolving pan, gather it, and pass it through a conjugation device such as a drum or kennel type, Wind it up in a small frame.
The role of the conjugation device in color reeling is large, and it relates to the adjustment of the number of yarn twists and the stabilization of the color of raw silk. In particular, in the case of heterogeneous color mixing, twisting and conjugation with an impeller is more effective than a Kennel conjugation device in order to produce a stable color and iridescent effect. Therefore, from this, the reeling machine can bring out the characteristics of the raw silk better. During spinning, in order to stabilize the fineness and color, if the oak or thin skin wrinkles appear, the wrinkles of that color are joined. The colored cocoon obtained as described above was obtained by spinning red cocoon (sample 1): blue cocoon (sample 2): light peach cocoon (sample 3) at a ratio of 15 grains: 15 grains: 4 grains. Raw silk is glossy purple, and an enlarged photograph of this raw silk bundle is shown in FIG.

(4) Silk Knitted Fabric Further, FIG. 2 shows an enlarged photograph of a silk knitted fabric woven with a plain knitting (tengu) using the raw yarn shown in FIG. A glossy chiffon with a complex shade was obtained.

Dyeing process Dyeing was performed by the same method as described in Example 1 using the following dye and solvent.
Raw material: 1kg (Gunma 200) 1kg (1,000 dried rice cakes)
Dye Blue high fastness oil-soluble dye (trade name: VALIFAST BULE
2606, Orient Chemical Industry Co., Ltd.) 5g
Solvent acetone 550ml
Methanol 250ml Mixture 1000ml
200 ml of ethyl acetate
As in Example 1, a color shade (sample 4) dyed blue was obtained. The dye was changed to a red high fastness oil-soluble dye (trade name: VALIFAST RED 2303, manufactured by Orient Chemical Industry Co., Ltd.), and dyeing was carried out to obtain a reddish color (sample 5). Boiled rice cake was performed in the same manner as in Example 1.

Spinning method This embodiment aims at spinning untwisted ribbon-like vertical stripe raw silk. Ribbon-like vertical stripe raw silk is put into a reversing pan with a cocoon that has come out of the yarn mouth, and a metal hair shaving is used as a conjugating device. As described in Japanese Patent No. 2936472, the conjugated raw silk after passing through the kennel twist, Pressure is applied to the yarn through the nip point of the roller to bring the cocoon yarn into close contact with each other, and the conjugated raw yarn is wound into a small frame after drying as a ribbon having a flat cross section.
180 white wrinkles (uncolored wrinkles): 50 red wrinkles <Sample 5>: Conjugated raw yarn obtained by spinning at a ratio of 50 blue wrinkles (Sample 4) is a ribbon having a gloss of white: red: blue It is a raw silk.

  During spinning, in order to stabilize the fineness and color fringes, if the Ochio and thin skin folds appear, the folds of that color are joined. This raw silk is only a flat raw silk if the denier is thin, but if it exceeds 700d, the color of the vertical stripes is emphasized, and it becomes a ribbon-like raw silk with a unique wave. Further, even when a plurality of wrinkles dyed in different colors are reeled by this method using the method of Example 1, a glossy ribbon-like raw yarn that cannot be expressed by a normal dyeing method can be obtained.

Silk Knitted Fabric Further, FIG. 3 shows an enlarged mesh view of a silk knitted fabric knitted by flat knitting using the ribbon-like raw yarn obtained as described above. A chiffon with a beautiful color change with a sharp feeling was obtained. The characteristics of raw silk and silk fabric obtained by the methods of Examples 1 and 2 are characterized by the original silky feeling and the color that cannot be expressed by normal dyeing.

In the present invention, since the center part of the silk thread is dyed before scouring, it is made into a hard texture without scouring according to the use, or a soft thin silk with a complex color, Products that can be used in various directions can be obtained. Moreover, in this invention, it is excellent in fastness and can color a raw silk stably. Examples of products using the raw silk according to the present invention include all knit products such as organdy stalls, shawls, tank tops, pullovers, and the like. In addition, products that overturn conventional wisdom such as color production machines, complex color fringes, and belts can be expected.

A is an enlarged photograph of a raw yarn bundle according to Example 1 of the present invention. 2 is an enlarged photograph of a chiffon fabric knitted with the raw silk shown in FIG. It is a mesh enlarged photograph of silk knitted fabric knitted by plain knitting using raw silk ribbon.

Claims (4)

A method for dyeing cocoons characterized by immersing the cocoons in a solution of an azo dye or phthalocyanine dye in an organic solvent to dye the fibroin protein at the center of the cocoon yarn . Cocoons, and the azo-phthalocyanine dye is immersed in a solution obtained by dissolving in an organic solvent, to stain the fibroin protein in the central portion of the yarn cocoon, then Nimayu and method for producing a dyed raw silk to reeling. Multiple cocoons are dyed by immersing them in a solution of different azo and phthalocyanine dyes in an organic solvent, and several cocoons in which the fibroin protein in the center of the cocoon thread is dyed in different colors are boiled simultaneously And dyed silk knitted fabric made of raw silk obtained by spinning. Cocoons were stained by immersing the azo-phthalocyanine dye to a solution in an organic solvent, a cocoon fibroin protein in the central portion of the yarn cocoons were stained, and Nimayu while leaving the sericin, A dyed silk knitted fabric made of raw silk having sericin obtained by spinning.

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