JPH062993B2 - Silk dyeing method - Google Patents

Description

The present invention relates to a method for dyeing without impairing the original texture of silk.

[Conventional technology]

Conventionally, silk from which sericin has been removed by scouring is a cloth, or with a device, because of the fibrillation of fibroin that occurs due to contact under wet conditions, it was not possible to avoid the occurrence of rubbing and folding, so hanging during dyeing, I had to rely on methods such as star dyeing machines, jigger, and beam.

For this reason, silk fibers have been modified, and there is a method (for example, Japanese Patent Laid-Open No. 64-6175) of preventing rubbing and breaking by processing with, for example, epoxide.

[Problems to be Solved by the Invention]

However, in the range disclosed in the above-mentioned prior art, a sufficiently soft original texture of silk is still not obtained, and a means for freely dyeing has not been disclosed.

On the other hand, the jet dyeing machine developed from Wins is a machine that uses the flow of the dyeing solution to smoothly move the cloth in the bath and prevent rubbing, folding, rope wrinkles and entanglement,
It is used for dyeing woven and knitted fabrics of cotton and wool, including synthetic fibers, and the low bath ratio and rapid progress are progressing. Recently, not only liquid flow by jet but also air flow combined machine has appeared. There is.

However, the present situation is that it is hardly applied to silk.
This is because as long as ordinary silk fibers are used, rubbing and breaking will occur even when using a jet dyeing machine.

The present inventors, as a result of earnest research, dyed silk fibers modified with epoxide with a jet dyeing machine,
The present invention has been accomplished by discovering an epoch-making method that complements each other's defects, maintains the original texture of silk, and enables rational dyeing without rubbing or breaking.

[Means for solving problems]

The present invention applies an aqueous solution containing a water-soluble epoxy compound and a catalyst to a 5 wt% sodium hydroxide aqueous solution at 65 ° C.
The silk fiber modified to have an alkali solubility of 20% by weight or less when dipped for 60 minutes in a dyeing machine is dyed by a jet dyeing machine.

The modified silk fiber referred to in the present invention refers to JP-A-64-617.
The water-soluble epoxy compound used in the present invention is modified with an epoxide according to the method disclosed in Japanese Patent No. 5 or the like, and ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, sorbitol, polyglycerol, Mention may be made of pentaerythritol, tris (2hydroxyethyl) isocyanurate, trimethylolpropane, neopentyl glycol, phenol ethylene oxide, lauryl alcohol ethylene oxide mono, and polyglycidyl ether. However, it is preferable to use a water-soluble epoxy compound having a water-soluble rate of 100% from the viewpoint of evenness of dyeing and good dyed surface. Water solubility 1 here
The term "00%" means that the dissolution rate is 100% when the required amount of the epoxy compound is dissolved in water at room temperature. Therefore, diglycerol triglycidyl ether, triglycerol triglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, phenol ethylene oxide glycidyl ether (additional mol number of ethylene glycol 5), lauryl alcohol ethylene Oxide glycidyl ether (the number of moles of ethylene oxide added is 15) and the like are preferable. The amount of the water-soluble epoxy compound applied varies depending on the epoxy equivalent, etc.
0% by weight, preferably 3 to 10% by weight, 3 to 50% by weight, preferably 6 to 40% by weight in the pad steam method, the pad dry steam method and the pad dry bake method, and 5 in the cold batch method. ˜50 wt%, preferably 10-40 wt%.

The catalyst that can be used in the present invention, a neutral salt, a weak alkaline salt, an alkaline salt, an acidic salt, an alkali metal hydroxide,
Ammonia water and amines. As the neutral salt, sodium and potassium salts of sulfuric acid, hydrochloric acid, nitric acid, thiocyanic acid and thiosulfate are preferable, and as the weakly alkaline salt, tartaric acid, citric acid, acetic acid, propionic acid and sodium hydrogen carbonate and hydrogen carbonate are preferable. As the alkaline salt, sodium salts and potassium salts of carbonic acid, silicic acid and aminopolycarboxylic acid are preferable, as the acidic salt, magnesium chloride is preferable, and as the amines, ethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine, m -Phenylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, 2-methylimidazole and dimethylaniline are preferred. The catalyst preferably has a pH of the processing liquid of 9 or higher. The amount of salt used is generally 0.5 to 20% by weight, preferably 1 to 15% by weight, based on the total weight of the processing liquid.

As a processing method for epoxy processing, a dipping method, a pad steam method, a pad dry steam method, a pad dry bake method, or a cold batch method can be used, but in the dipping method, for example, 50 to 110 ° C. , Preferably 6
Process at a temperature of 0-95 ° C. In the pad steam method, for example, after applying an aqueous solution of 50 to 200% by weight, preferably 80 to 120% by weight, to silk fiber, 120
Steaming is performed with saturated steam at a temperature equal to or lower than 0 ° C, preferably lower than 110 ° C. In the pad dry steam method, for example, 50 to 100% by weight, preferably 80 to 1% by weight based on the silk fiber.
After applying a 20% by weight aqueous solution, it is dried at a temperature of 50 to 100 ° C. and then steamed with superheated steam of 150 ° C. or lower or saturated steam of 120 ° C. or lower, preferably 110 ° C. or lower. In the pad dry bake method, for example, 50 to 200% by weight, preferably 80 to 120% by weight of an aqueous solution is applied to silk fiber, and then 50 to
It is dried at a temperature of 100 ° C. and then heat-treated with hot air of 180 ° C. or lower, preferably 170 ° C. or lower. In the cold batch method, for example, after applying an aqueous solution of 50 to 200% by weight, preferably 80 to 120% by weight, to silk fiber, it is kept at room temperature, preferably 1
Leave at 0-40 ° C for 20-50 hours. In the present invention, it is possible to use any of these methods, but the dipping method is particularly excellent in that the reforming efficiency and the coarse hardness of the texture are small, and reforming using a Jigger or a jet dyeing machine is possible. It is particularly preferable in terms of uniformity.

According to the present invention, by such a method, the alkali solubility is modified to 20% by weight or less. Alkali solubility is 5% by weight of NaOH
The weight loss% of silk when treated with an aqueous solution at 65 ° C. for 60 minutes is 0 weight% when the weight is not reduced, and 100 weight% when completely dissolved.

The modified silk fiber is then dyed with a jet dyeing machine.

As a jet dyeing machine, one that is filled with the dyeing solution in the entire dyeing machine, one that has a space in part, a vertical type, a horizontal type, a fabric rope that circulates in the vertical direction, a horizontal Circulating thing, cloth driven by jet jet, dyeing liquid overflow driven, combination of both, reel assisted drive, reelless, tank structure, tube structure There are various structures such as single, single unit, multi-unit, etc., any of which can be applied, but in particular, the whole dyeing machine is filled with the dyeing solution, the fabric circulates in the vertical direction and the overflow of the dyeing solution. A tube structure in which the cloth is driven by the combination of the jet jet and the jet jet is preferable from the viewpoint of the feeling after dyeing.

As the dye, reactive dyes, acid dyes, metal complex salt dyes, acid mordant dyes and the like can be used. In the case of reactive dyes, vinyl sulfone type, vinyl sulfone monochlorotriazine type, monochlorotriazine type, trichloropyrimidine type and nicotinic acid are used. The use of the triazine type also has the effect of improving the dyeing fastness to chlorine water.

Dyeing conditions are preferably slightly milder than when dyeing synthetic fiber products. For example, the running speed of the object to be dyed in the dyeing machine is 30 to 50 m / min compared to 100 m / min or more of synthetic fiber products. It is good to loosen. Further, when an acid dye or a metal-containing dye is used, it is preferable to use a small amount of a low-foaming surfactant so as not to generate bubbles and cause unevenness, or it is preferable not to use a surfactant in combination, or a weak alkaline. ~ It is recommended to perform dyeing in the neutral range (pH 8 to 7). When a reactive dye is used, it is preferable to add each of Glauber's salt and soda ash separately, and further divide them in order to improve the leveling property.

The form of the silk fiber is not particularly limited, and woven fabric, knitted fabric and the like can be used, but plain woven fabric and twill woven fabric are particularly preferable.

[Action]

In the present invention, jet dyeing is applied to highly modified silk fibers having an alkali solubility of 20% by weight or less, so that rubbing hardly occurs during dyeing. Moreover, the texture of the highly-modified silk fiber before dyeing is hard as it is, but it becomes a soft texture due to the rubbing effect in the jet dyeing, and an epoxy-processed dyed product having the original texture of silk can be obtained.

〔Example〕

Example 1 A plain woven fabric using silk spinning 140 count double yarn (density 114 yarns / inch) as weft and silk spinning 66 count single yarn (density 89 yarns / inch) as weft yarns was scoured by an ordinary method, and then ethylene was used as an epoxide. Glycol diglycidyl ether 3
0 g / (water solubility 100%), using a working solution of sodium sulfate 100 g / dissolved in water as a catalyst, using a jigger as a processing device, starting from a temperature of 40 ° C. 90 up to 90 ℃
It was modified at 60 ° C. for 60 minutes. The alkali solubility was 15. The modified silk was dyed black with an acid dye using Rapid Uniace Reelless Jetwins (manufactured by Nippon Dyeing Machine). It was possible to dye uniformly without rubbing or breaking. The texture was also flexible. An electron micrograph of this dyed cloth is shown in FIG. No fibrillation has occurred. For comparison, an unmodified cloth of the same type (alkali solubility 8
0) was used and dyed in the same manner as the modified cloth. Rubbing, breaking, and wrinkling were serious, and the color was far from black. The texture was also coarse and hard. An electron micrograph of this dyed cloth is shown in FIG. Fibrillation is intense.

Example 2 Raw warp 30d single yarn (density 156 / inch) as weft 3/2 1d yarn (density 104.5 / inch) as warp
After scouring a flat crepe using a conventional method, as an epoxide, polyethylene glycol (n = 13) diglycidyl ether 200 g / (water solubility 100
%), Using a working liquid in which 100 g / sodium chloride is dissolved in water as a catalyst, and using a mangle as an apparatus,
The processing liquid was applied to the cloth (drawing ratio 80% by weight). The cloth was wound on a roll and sealed with a polystyrene sheet so as not to evaporate water, and the roll was rotated in a room controlled at 30 ° C. for 24 hours for modification processing. The alkali solubility was 16.5. The modified silk was dyed in dark blue with a metal-containing dye using a loco-type jet dyeing machine (manufactured by Hokuriku Kakoki). It was possible to dye uniformly without rubbing, breaking, or wrinkling of the rope. The texture was also good. An electron micrograph of this dyed cloth is shown in FIG. No fibrillation has occurred.
For comparison, the same type of unmodified cloth (alkali solubility 72) was used and dyed in the same manner as the modified cloth. There were scratches, folds and wrinkles, and the dark blue was whitish and was not of commercial value.

Example 3 Silk warp 140 count twin yarn (density of 124 yarns / inch) is used as warp and silk spin 140 count twin yarn (density of 106 yarns / inch) is used as weft yarn.
Fuji silk using (inch) was scoured by a conventional method, and then polypropylene glycol (n = 3) diglycidyl ether 200 g / (water solubility 100%) was used as an epoxide.
The working fluid prepared by dissolving 100 g / sodium diethylenetriaminepentaacetate in water was used as the catalyst, and the working fluid was applied to the cloth using the mangle as the device (squeeze ratio 7
5%). After drying once, steaming was performed for 30 minutes with saturated steam at 100 ° C. for modification processing. The alkali solubility was 12.9. The modified silk was dyed red with a vinyl sulfone monochlorotriazine type reactive dye using a vertical circular jet dyeing machine (manufactured by Hisaka Seisakusho). It was possible to dye uniformly without rubbing, breaking or wrinkling. The texture was the same as silk. For comparison, the same processing was carried out using an epoxide amount of 100 g /, but the alkali solubility was 35, and when dyed in the same manner, rubbing occurred and it was not commercial value.

Example 4 A Georgette crepe using raw yarn 3 / 17d (density of 124 yarns / inch) as warp and raw yarn 3 / 17d (density of 109 yarns / inch) as weft yarn is scoured by a conventional method,
Dichlorotriglycidyl ether 20 g / (water solubility 100%) as an epoxide, sodium citrate 100 g / as a catalyst is used as a processing solution in water, and an atmospheric pressure roco jet jet machine (manufactured by Hokuriku Kakoki) is used as a processing device. Start at 40 ° C with 90 minutes in 25 minutes
The temperature was raised to 90 ° C. and reforming was performed at 90 ° C. for 60 minutes. The alkali solubility was 18.1. After soaping, the same equipment was used to dye black with chrome dye. It was possible to dye uniformly without rubbing, breaking or wrinkling. The texture was soft.

Example 5 After kneading a knit using raw silk by a conventional method, triglycerol triglycidyl ether 200 was prepared as an epoxide.
The working liquid was prepared by dissolving 20 g / (2% methyl imidazole) of g / (water content 100%) in water as a catalyst, and mangle was used as a device to apply the working liquid to the cloth (squeezing ratio: 82%). After being dried once, it was cured at 180 ° C. for 30 seconds for modification processing. The alkali solubility was 19.4. This modified silk was dyed beige with a gold-containing dye using a Rapid Uniace-RX type jet dyeing machine (manufactured by Nippon Dyeing Machine). It was possible to dye uniformly without rubbing, breaking or wrinkling. The texture was good without unevenness. Also, as an epoxide, glycerol diglycidyl ether 20
g / (water-soluble rate 99%), undissolved matter was generated, so the same modification processing was carried out using a processing solution prepared by dissolving 50 g / isopropyl alcohol as a solubilizing agent and 20 g / methylene imidazole 20 g / catalyst in water. . The alkali solubility was 19.8. The modified silk was dyed in the same manner. It could be dyed without scratches, folds or wrinkles, but it was slightly mottled and the dyed surface was irritable. The texture was uneven.
For comparison, an unmodified cloth (alkali solubility 77) was also dyed in the same manner, but rubbing, breaking, and rope wrinkling occurred, the color was whitish, and the texture was coarse and hard, and thus had no commercial value.

Example 6 A plain woven fabric using 140-twisted silk spinning yarn (density of 105 yarns / inch) as warp and 140-twisted silk yarn of 140 spinning yarn (density of 88 yarns / inch) as weft is scoured by a conventional method, and then ethylene is used as an epoxide. Using glycol diglycidyl ether 30 g / (water solubility 100%), sodium sulfate 100 g / as a catalyst in water, and a jigger as a processing device, starting from a temperature of 40 ° C., every 10 ° C. The temperature was raised to 90 ° C. by the step temperature rise, and the modification processing was performed at 90 ° C. for 60 minutes. The alkali solubility was 17. This modified silk is treated with a Rasta type jet dyeing machine (manufactured by Kitagawa Kogyo) using a gold-containing dye and Glauber's salt, and a neutral bath (p
It was stained blue with H8). The flow rate of the cloth at the time of dyeing (surface speed of the reel) was 30 m / min. It was possible to dye uniformly without rubbing or breaking, and the texture was close to that of regular products. For comparison, some rubbing occurred when the cloth flow rate was set to 130 m / min. For comparison, when dyeing was performed using a jigger instead of a jet dyeing machine, rubbing did not occur, but it was rough and hard. The dyed surface was also patchy. When soap was added and dyed in a weak alkaline bath (pH 9.2), the mottledness disappeared, but the density became lighter. The texture was still rough.

〔The invention's effect〕

According to the present invention, it is possible to obtain a silk dyed product which is free from rubbing and does not impair the original feeling.
In addition, the management of the processing steps is easy and extremely useful.

[Brief description of drawings]

1 to 3 are electron micrographs (120 times each) of the surface of the dyed product obtained by the present invention, showing the shape of the fiber.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location D06M 11/56 13/352 15/53 D06P 5/00 A 9160-4H // D06M 101: 12 D06M 13/36 7199-3B 3/04 A

Claims (1)

[Claims] 1. An aqueous solution containing a water-soluble epoxy compound and a catalyst is applied to a 5% by weight sodium hydroxide aqueous solution to obtain 65
Alkali solubility of 20% by weight when immersed for 60 minutes at ℃
A silk dyeing method, which comprises dyeing the following modified silk fibers with a jet dyeing machine.