JPH0635715B2 - High-fastness dyeing method for protein fiber products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a fiber product composed of protein fibers such as silk and wool, which are treated with an epoxy compound and have excellent wash and wear properties (WW properties). The present invention relates to a method of imparting a color possessing excellent dyeing fastness. More specifically, by introducing a cross-linking bond into the protein fiber in a wet state by heat-treating a protein fiber product saturated with an aqueous solution of a neutral salt in an organic solvent solution containing an epoxy compound and hardly soluble in water. A textile product with a high degree of WW property is coated with a color paste containing a leuco salt of a vat dye, and is applied and dried by a method such as padding or ironing, or a roller or screen type is used to apply the color paste according to the design. The present invention relates to a method for obtaining a dyed product with excellent color development and high fastness by printing, drying, steaming and post-treatment.

[Conventional technology]

Originally, clothing made of protein fibers such as silk and wool, which prioritize sensory characteristics, has been given special consideration in its handling compared to apparel made of chemical fibers that have been developed by pushing functional characteristics over the entire surface. This is well known. In particular, the washing of protein fiber products often depends on dry cleaning by a specialist, and even in home washing, a special detergent is used and push washing with warm water is recommended. It is a well known fact that these are mainly caused by the structural characteristics of the protein fiber or the morphological stability of the apparel composed of the fiber. For example, it has been generally pointed out that in the case of a silk fiber product, a remarkable damage or shrinkage of the appearance due to rubbing, and in the case of a wool fiber product, rough hardening and shrinkage of the feel due to felting.

However, these drawbacks are modified by a two-phase method in which silk fiber saturated with an aqueous solution of a neutral salt is heated in an organic solvent solution containing an epoxy compound (Japanese Patent Publication No. 52-38131) and treated with an epoxy compound. A method of modifying protein fibers with a cellulose-reactive crosslinking agent (Japanese Patent Publication No. 63-66).
947) and the like, and is applied to JP-A-63-227856.
It is well known that the method for treating a knitted fabric made of silk fibers and the apparatus therefor disclosed in Japanese Patent Publication has been greatly improved and is called "washable silk" and is widely used in practice.

As a matter of course, it has been desired for these protein fiber products imparted with excellent WW properties to increase the chances of receiving general household washing in practical use, and to further enhance the dyeing fastness of the fibers. .

Originally, the dyeability of protein fibers treated with epoxy compounds was improved for supermilling type acid dyes or metal complex salt dyes, etc., which are relatively fast to these protein fibers, and their fastness is also improved. However, it is not always considered to be a satisfactory level under the actual washing conditions that are allowed from the viewpoint of the morphological stability improved by imparting the WW property. Therefore, various dyeing fastness improving treatments such as a fixing treatment of the dyed product with the dye or a change of soaping conditions have been investigated, but a satisfactory fastness level can be reached without impairing the sensory characteristics peculiar to the protein fiber. The current situation is that it cannot be done. Focusing on improving the alkali resistance of protein fibers treated with epoxy compounds, research on dyeing and printing with reactive dyes is also ongoing, but the tendency of dyeing property deterioration due to treatment is observed. In addition, no method has been found for obtaining practical fastness satisfying the above-mentioned washing conditions.

On the other hand, it shows a clear hue and the highest fastness, and is also recommended depending on the chemical structural characteristics of each so-called vat dye composed of anthraquinone-based and indigo-based dyes that have been used for fibrous fibers. In any of the dyeing treatment methods, even under the condition that caustic soda and hydrosulfite are used in combination, even the protein fiber treated with an epoxy compound has a tendency of color development and shrinkage and embrittlement of the fiber during the dyeing or printing process It is recognized that its application is extremely difficult due to rough curing and the like.

Of course, the traditional method of applying the leuco compound of the indigo-based vat dye, which dyes fibrin fibers from a neutral bath, to protein fibers such as wool and silk from an acidic bath can also obtain a hue of a light color. This level is only reaffirmed for epoxy treated protein fiber products. Also,
Developed as a dyeing method for acetate fibers, and then applied to synthetic fibers such as vinylon and polyester, an alkaline reducing solution of anthraquinone-based vat dye is neutralized in the presence of a dispersant to produce colloidal free vat acid. The so-called vat acid dyeing method of converting to leuco compound on the fiber with caustic soda and hydrosulfite to give affinity to the fiber for dyeing, and then oxidative coloring is treated with epoxy compound It has been confirmed that the product cannot be out of the same level as the untreated protein fiber, and its practical value is significantly inferior to the color development of the existing protein fiber obtained from the acid dye.

[Problems to be solved by the invention]

As described above, it is a protein fiber product modified with an epoxy compound that possesses a significantly improved WW property, but it has excellent color stability that can withstand the washing conditions applied due to improved morphological stability. It has been posed as a great difficulty that the overall consumption performance as an apparel is remarkably saved because a dyeing method that possesses a certain degree is not found.

[Means for solving problems]

The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, paying attention to the improvement in chemical resistance of the protein fiber treated with the epoxy compound, and showing the highest vivid hue for the fibrous fiber. The present invention has been accomplished by extensively studying a dyeing method using a vat dye showing fastness.

A so-called pre-reduced Rongalit-potassium method utilizing a color paste containing a leuco salt used for printing as a coloring method with a vat dye, a finely divided vat dye is used, and potassium carbonate or sodium carbonate and a low temperature are used. A so-called post-reduction Rongalite-potassium method that uses a color paste containing an unreduced dye containing stable rongalite, and a so-called alkali that prints a color paste containing only vat dye, and then heats it by applying an alkali and a reducing agent. -The blotch method is known. However, most of the coloring methods for these fibrous fiber products are replaced by reactive dyes which have excellent color developability, good fastness and extremely high productivity. However, the Rongalit-Potasium method is suitable for high-value-added processing in high-mix low-volume production, although it has some difficulties in quality control. It is only done.

The present invention is mainly applied to the fibrous fiber, and the color paste containing the leuco salt of vat dye, which has not been recognized as the application value in the conventional protein fiber products, is treated with the epoxy compound to improve the WW property. By observing that it acts on white fiber products in an extremely stable state and can reproduce color development comparable to that of acid dyes and high fastness on fibrous fibers, we have found optimal conditions based on that knowledge. It is a thing.

The protein fiber product treated with the epoxy compound referred to in the present invention is a protein fiber treated by the method described in Japanese Patent Publication No. 52-38131, which is obtained by the reaction determined from the weight difference before and after the treatment. Those with a weight increase of 3% by weight or more are suitable. That is, in terms of color developability and fastness, when it is 3% by weight or more, the difference from the untreated protein fiber becomes remarkable. Further, 5% by weight or more is preferable in order to prevent the decrease in strength of the fabric due to dyeing.

Further, a color paste containing a leuco salt of vat dye is prepared separately by reducing vat dye in the presence of potassium carbonate or sodium carbonate and Color Index (CI) reducing agents 2, 3, 4 and 6 alone or in combination. It is obtained by mixing with the alkali resistant sizing agent. The amount of alkali used should be at least 4% by weight and at least 8% by weight of reducing agent in the color paste, preferably 6 to 10% by weight for the former and 8 to 15% by weight for the latter. Is.

In particular, alkali reduces the effect on humidity depending on the work environment, such as sodium carbonate in the summer when the humidity is high, and potassium carbonate in the winter, and also has a relative alkali resistance compared to silk. In the case of extremely low wool, it is extremely important in production control to reduce the total amount of alkali and to use organic amines such as triethanolamine having a weak reducing property together. On the other hand, the reducing agent is a water-insoluble reducing agent 4 (formaldehyde sulfoxylate zinc, acid can be used in order to maintain the reduction stability of vat dye leuco salt in the paste layer printed and dried on the protein fiber product. However, the reducing agent 6 (formaldehyde sulfoxylate zinc, water-soluble) is substantially insolubilized in the presence of an alkali, and the same behavior can be obtained, so that it can be conveniently used.

As the sizing agent to be mixed and used, alcal-resistant sizing agents such as highly etherified carboxymethyl cellulose, guar gum, locust bean gum or modified starch can be used, but in order to maintain the reduction stability of the vat dye leuco salt in the dry color paste. Since it is desired that the paste layer be thicker, a sizing agent of 10% by weight or less of the solid content of the original paste should be avoided. It is desirable to select a sizing agent.

In addition, coexistence of glycerin, thiodiethylene glycol or urea as a hygroscopic agent, an alkali salt of pyrrolidonecarboxylic acid as a moisturizing component, and a permeation and leveling agent cannot be prevented in order to improve the flow characteristics of the color paste.

The protein fiber product coated or printed with the above-mentioned color paste is dried and then steam-heat treated by a conventional method. As steaming, either normal pressure steam, high pressure steam or high temperature steam can be applied, but it is necessary to accelerate dyeing at 103 ° C or lower. When the temperature is 103 ° C. or higher, not only the color is remarkably deteriorated due to overreduction, but also the fastness and strength are deteriorated. This tendency is most remarkable in the case of high temperature steaming. Dyeing is completed by steaming for 10 to 30 minutes. The steamed protein fiber product is subjected to oxidation treatment in an acidic warm bath of hydrogen peroxide, then soaped, washed with hot water, and arranged and finished according to a conventional method.

Problems such as embrittlement due to dyeing, reduction of gloss and disappearance of silking that occur when the above process method is applied to untreated protein fiber products are all solved with regard to epoxy-treated protein fiber products. In addition, the obtained dyed product has an extremely clear and high coloring density compared to the untreated protein fiber product, and it is possible to obtain a quality that exceeds the coloring hue and density dyed under optimum conditions for fibrous fiber. Can be confirmed.

It can also be confirmed that the dyeing fastness on the protein fiber product is comparable to the fastness on the fibrous fiber.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 A 10% by weight aqueous solution of thiocyanpotassium was saturated with a wool surge surged by a conventional method, and 10 parts of glycerin diglycidyl ether and 1,1,1-trichloroethane 90 were added.
In a reaction solution consisting of parts, the mixture is treated at 70 ° C. for 2 hours, and post-treated and finished according to a conventional method. The weight increase due to the treatment of the wool surge was 6.5%. These untreated and epoxy-treated wool surges were printed with A and B white pastes having the following compositions using a screen mold, respectively, and dried.
After steaming at 00 ° C for 20 minutes in normal pressure steam and lightly washing with water, immediately dissolve 5g of hydrogen peroxide, 2g of 98% acetic acid and 1g of nonionic surfactant in 1 of water in an oxidation treatment bath at 50 ° C. Color develop for 5 minutes. After that, soaping, washing with hot water, and washing with water are performed according to the usual method.

(1) A paste composition CI vat yellow 2 2.0% sodium carbonate 6.6 potassium carbonate 3.4 thiodiethylene glycol 1.5 CI reducing agent 4 9.3 guar gum 8.7 highly etherified CMC 10.9 preservative 0 .1 Water 57.5 (2) B paste composition CI Bat Green 1 3.0% sodium carbonate 2.0 triethanolamine 3.0 sodium pyrrolidonecarboxylate 2.0 CI reducing agent 4 5.0 CI reducing agent 6 5 0.0 Processed starch 12.6 Locust bean gum 7.2 Preservative 0.05 Water 60.15 Untreated wool surges printed with both A and B paste, and the fibers were significantly embrittled after drying. While it was confirmed that it could not be put to practical use at all, in the epoxy treated wool surge, embrittlement was observed with the A glue, and defects such as rough hardening and shrinkage of the texture were observed, but B By using the paste, it is possible to obtain a dyed product which has an excellent hue and a high density and which retains the characteristics such as texture and luster peculiar to wool. The dye fastness is confirmed to be the level obtained on the fibrous fiber.

Example 2 Example 1, B Color paste having a size composition of sodium carbonate reduced to 1% and triethanolamine reduced to 1.5% was diluted by 20% and untreated and treated with an epoxy (the weight increase due to the treatment was 3.5% by weight). %) Wool muslin is squeezed and color development is carried out in accordance with Example 1 to obtain a dyed product in which epoxy-treated muslin is considerably superior in hue depth. However, untreated muslin has a remarkable brittleness of fibers in a drying process such as color paste ironing, and it often breaks during withdrawal from the printing table, which makes workability extremely difficult.

The same phenomenon can be confirmed from a color paste using CI Bat Brown 5 to CI Bat Blue 48 or the like, which has a relatively good color developability to an untreated protein fiber product.

Example 3 CI bat red 1 was prepared according to Example 1, A paste composition.
Using 0% of the color paste, it is printed on silk decine, dried, and colored and arranged in the usual manner. Color development on epoxy treated decyne (increased amount 4% by weight) becomes remarkably clear as compared with untreated decyne, while the latter eliminates silking and coarsely cures, while the former maintains silk-specific performance. Can be confirmed.

Example 4 A 14 Nm silk silk twill bleached in accordance with a conventional method was filled with a 1N aqueous solution of sodium acetate at a squeezing rate of 100%, and was placed in a 6 wt% perchloroethylene solution of ethylene glycol diglycidyl ether at 65 ° C. Heat treatment for 3 hours 10
An epoxy treated cloth with a weight% increase was obtained. Separately, mercerized cotton broad prepared in a conventional manner was prepared, and a color paste composed of CI bat violet 1 according to the A paste composition detailed in Example 1 was applied to three kinds of fabrics including untreated silk. Printing, drying, and steaming using high temperature steam at 102 ° C. for 15 minutes, oxidative coloring, post-treatment, and finishing, and comparing the coloring hues are as follows.

That is, it can be confirmed that the color density of the vat dye on silk, which is generally inferior in color development to cotton, is remarkably improved by the epoxy treatment. It is also well supported by the fact that the bluish color of the epoxy-treated silk is similar to that of cotton from b, and that the reddishness of the epoxy-treated silk is more emphasized than cotton and expresses a clear purple color, as inferred from a. There is. Of course, it can be confirmed that the epoxy treatment sufficiently improves the defects such as rough hardening of the texture, shrinkage, embrittlement, and disappearance of silk squeal with respect to the untreated silk. The dyeing fastnesses of all three are outstanding, and the epoxy-treated silk has been given washable characteristics in terms of morphology and fastness.

[Curing of invention]

The coloring hue of the dyeing product that can be imparted by the method of the present invention is a vivid color comparable to the hue of the acid dye that has been frequently used in protein fiber products, and its dyeing fastness is the highest obtained on fiber. It was confirmed that the same level of robustness as was obtained. Therefore, the dyeing fastness washable property is added to the morphological washable property achieved by the epoxy treatment, and the constraint on the consumption performance of the protein fiber product that emphasizes the WW property can be eliminated.

Claims (1)

[Claims] 1. A high-performance protein fiber product, which is characterized in that a fiber product composed of a protein fiber treated with an epoxy compound is dyed or printed with a color paste containing a leuco salt of a vat dye. Fastness dyeing method.