JPS6361428B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application Field The present invention relates to a method for processing protein fibers such as silk and wool, and more specifically, to processing protein fibers in the form of cloth, thread, cotton, paper, and powder, and structures containing the same with disperse dyes. The present invention relates to a method for modifying a system structure. Therefore, it will greatly contribute to the expansion of applications in a wide range of fields such as medical care, architecture, and information, as well as clothing-related industries that use these structures. Prior Art Highly hydrophilic protein fibers such as silk and wool have essentially no affinity for disperse dyes;
Due to the recent advances in printing technology and the demand for expanded uses for protein fibers, there has been a strong desire to develop protein fibers that can be used in dry transfer printing. In practical terms, there are great expectations for dry transfer printing of blended structures with other synthetic fibers such as polyester. To deal with these problems, a method of treating silk fibers with polyhydric alcohol (Special Publication No. 47-43156)
has been proposed, and it is widely known that dyeing with disperse dyes also occurs when a large amount of highly hydrophobic vinyl monomers is graft-polymerized. However, these methods do not provide clear color development and are also poor in color fastness, especially dry cleaning and wet rubbing fastness, which are important in practice. As a method to improve these problems, a method has been proposed in which graft polymerization with a vinyl monomer is performed and then treatment with hexamethylene diisocyanate (Japanese Patent Application Laid-open No. 156883/1983), but in the case of silk and wool fibers, the treatment The disadvantage is that the texture, moisture absorption, and wrinkle resistance of the fibers are adversely affected. In addition, protein fibers treated with carboxylic acid anhydrides or chlorides can be dyed with disperse dyes, but it was difficult to dye them in deep colors to a practical level [Nichisokuzo 49 (4) 302-306 (1980)]. Therefore, a method was proposed (Japanese Patent Publication No. 57-30185) in which a monocarboxylic acid is acylated with an anhydride or chloride and then a hydrophobic vinyl monomer is graft-polymerized. There were many practical disadvantages, such as the fact that the compound or chloride had to be used together with an expensive and highly water-absorbing solvent such as dimethylformamide or dimethyl sulfoxide, and under anhydrous conditions. In other words, these acid anhydrides or acid chlorides are easily hydrolyzed into carboxylic acids by trace amounts of water, reducing reactivity and preventing acylation of protein fibers, making process control difficult. Problems to be Solved by the Invention Protein fibers that are not dyeable with disperse dyes must be made dyeable with disperse dyes by some means, but first, a method of graft polymerizing vinyl monomers is not possible. Although disperse dye-dyeable hydrophobic monomers have to be grafted, their lack of affinity with protein fibers results in non-uniform intra-fiber deposition of the grafted polymer, leading to processing irregularities. It has become the cause. If a hydrophilic monomer is used, the graft polymer can be deposited relatively uniformly within the fiber, but there remain problems such as reduced dyeability with disperse dyes. Therefore, a method can be considered in which the protein fibers are first treated with a compound that has a high affinity with the protein fibers to block the hydrophilic functional groups in the protein fibers, and then a hydrophobic vinyl monomer is graft-polymerized. The method using the anhydride or chloride of carboxylic acid mentioned above falls into this category, but in addition to the drawbacks mentioned above, the hygroscopicity of the treated protein fiber is drastically reduced, making it unsuitable at least as a textile material for clothing. It becomes appropriate and the scope of use is limited.
The present inventors solved these problems and investigated a method for modifying protein fibers and structures containing protein fibers that would enable dry vapor phase dyeing to be as robust as synthetic fibers such as polyester. Completed the invention. Means for Solving the Problem When protein fibers and structures containing protein fibers are treated with various epoxy compounds in the presence of a neutral salt aqueous solution, amino groups, carboxyl groups, alcoholic and phenolic hydroxyl groups in the fibers are removed. It is known that this increases hydrophobicity and improves wrinkle resistance, yellowing resistance, etc. (Japanese Patent Publication No. 47-24199, 52-38131). In particular, wool is rich in amino groups, so the dye fastness and setting properties of oxidative dyes are significantly improved. Although this treatment allows protein fibers to be dyed with disperse dyes, it is difficult to dye them to a deep color that is practical. However, when a vinyl monomer is further graft-polymerized to protein fibers and structures containing protein fibers treated with epoxy compounds, 30%
It was found that vapor-phase dry printing is possible even with a certain degree of grafting rate, and that it exhibits sufficient fastness for practical use. That is, the amino groups, carboxyl groups, hydroxyl groups, etc. of protein fibers are blocked by the epoxy compound, increasing hydrophobicity, and the graft polymer is deposited uniformly within the fibers during the next graft polymerization. When dyeing with disperse dyes, the diffusion of the dye within the fibers and the number of dyed seats become uniform and increase, resulting in uniformly dark and strong dyeing. Since a modification effect that exceeded expectations was actually observed, it is thought that the combination of epoxy compound treatment and graft polymerization treatment produced a synergistic effect that could not be expected from the individual treatments or the method of treating the epoxy compound after graft polymerization treatment. It will be done. That is, the present invention provides a disperse dye dyeable method, which is characterized in that a protein fiber structure such as silk or wool or a structure containing protein fiber is treated with an epoxy compound, and then graft polymerized with a polymerizable organic monomer. A method for producing a type protein fiber structure or a structure containing protein fiber, and a method for producing a type protein fiber structure or a structure containing protein fiber dyeable with disperse dyes, such as a disperse dye, an oil-soluble dye, a basic dye, a benzine-soluble dye, or a mordant. The present invention relates to a dyeing method characterized by printing using at least one dye selected from dyes and vat dyes. The treatment with an epoxy compound in the present invention is
A known method (Japanese Patent Publication No. 47-24199, 52-38131) can be used. That is, a protein fiber structure or a structure containing protein fibers is impregnated with a composition containing various epoxy compounds in the presence of a water-soluble neutral or weakly basic metal salt, and then heat-treated by various methods. This allows processing with an epoxy compound without impairing the advantages of the structure. Catalysts for treating epoxy compounds used in the present invention are known catalysts, including alkali metals such as lithium, sodium, potassium, rubidium, and osmium, and alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium. A water-soluble neutral or weakly basic salt consisting of a cation and an anion such as fluorine, base, bromine, iodine, nitric acid, sulfuric acid, acetic acid, monochloroacetic acid, propionic acid, sulfite, cyanic acid, thiocyanic acid, thiosulfate, etc. , of a 1N aqueous solution
It is desirable that the pH is within the range of 5.5 to 9.0. These salts are dissolved in water and used alone or added to a composition containing an epoxy compound, but the concentration is generally 0.1 to 3N; if it is too low, the reaction promotion effect cannot be obtained, If it is too high, there is a risk that the structure will partially dissolve depending on the heat treatment conditions and the treated fiber structure, so sufficient care must be taken in adjusting the concentration of these salts. Generally, the range is preferably 0.1 to 0.5 when animal hair fibers such as wool and rabbit hair are included, and 0.5 to 1.5 when using silk fibers. The epoxide that can be used in the present invention has the general formula: (However, in the formula, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms or any organic residues that allow the compound of the formula to exist stably and do not interfere with the reaction with protein fibers, and are interconnected to form a ring. These organic residues include nitro, nitroso, cyano, isocyano, halogen, carboxyl, dithiocarboxyl, carbonyl, thiocarbonyl,
hydroxyl, amino, amide, alkoxyl,
Epoxy, sulfonyl, sulfanyl, imino,
Imide, phosphonyl, phosphinyl groups, and alkyl substituted or unsubstituted with these groups,
alkenyl, alkynyl, aralkyl, aryl, alkoxyl, aryloxyl, allyl,
It is a group such as allyloxyl). These include alkylene oxides, glycidyl ethers, glycidyl esters, epoxy acids and their esters and amides, glycidyl urethanes, glycidyl esters of sulfonic acid and phosphoric acid,
Included are epoxy silanes, epoxy alcohols, epoxy amines, halogenated epoxides, carbonyl epoxides, and the like. In addition, since this epoxy compound treatment method is carried out in the presence of the above-mentioned neutral or weakly basic salt aqueous solution, the protein fibers sufficiently expand, and as a result, the above-mentioned epoxy compound diffuses into the protein fiber structure. Since the reaction is carried out uniformly and quickly, the reaction proceeds uniformly. Therefore, as in the method of treating with carboxylic acid anhydride or chloride (Japanese Patent Publication No. 57-30185),
It is not the case that long chain compounds are inappropriate. These epoxy compounds can be used alone or in a mixture of two or more, but the number of epoxy groups in the epoxy compound molecule, the reactivity, and the interaction of the epoxy compounds should be considered, and the type of processed protein fiber It is important to select the appropriate reaction conditions depending on the intended use and to determine the appropriate reaction conditions. Such epoxy compounds can be used as they are, or may be dissolved in a suitable solvent. In other words, if it is water-soluble, it can be used directly as an aqueous solution, but if it is water-insoluble, it can be dissolved in a mixed solvent of water and a water-soluble solvent such as methanol, acetone, or dioxane.
Alternatively, it can be used as an emulsified dispersion by an appropriate method or dissolved in an appropriate non-aqueous solvent. The amount of the epoxy compound used varies depending on the type of protein fiber, tissue, etc., as well as the type of epoxy compound, but is 2 to 40%, preferably 6 to 20%, based on the weight of the protein fiber. In addition, in the treatment step with an epoxy compound in the present invention, protein fibers are impregnated in a formulation containing an epoxy compound as is known in the art, but protein fibers are coated with a spray or foam composition containing an epoxy compound and heat treated. It is. After drying,
As for heating methods other than dry heat treatment, all known heating methods such as steaming treatment and microwave irradiation treatment can be applied. The protein fiber structure or protein fiber-containing structure treated with an epoxy compound in this way is soaped and washed with water according to a conventional method, and then left as is or dried without being bleached in the next graft polymerization process. Furthermore, by using an aqueous solution in which a dye that does not cause any hindrance during transfer printing with disperse dyes is added at the same time as salt, it is possible to permanently modify protein fibers and dye them at the same time (Japanese Patent Publication No. 48-22874 , 49−3470). All known organic monomers that graft polymerize to protein fibers can be used to graft-polymerize protein fiber structures and structures containing protein fibers treated with epoxy compounds. Among the most useful ones, the general formula CH ₂ = CR ₁ CO ₂ R ₂ (wherein, R ₁ represents H or halogen, an alkyl group, and R ₂ represents hydroxyl, amino, halogen,
Groups such as alkyl, alkenyl, alkynyl, aralkyl, aryl, allyl, substituted or unsubstituted with groups such as alkoxyl, epoxy, carbonyl, carboalkoxyl, alkenyloxyl, alkanoyloxyl, thiocarbonyl, dithiocarboxyl, cyano, isocyano, nitro, etc. ester derivatives of acrylic acid and methacrylic acid represented by acrylic acid and methacrylic acid, such as methyl, ethyl, propyl, butyl, allyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, vinyl, propynyl, Examples include phenyl, benzyl, glycidyl, tetrahydrofurfuryl, hydroxyethyl, hydroxypalmityl, ethoxybutyl, methoxypropyl, ethylene glycol, and propylene glycol ester. Also, the general formula CH ₂ = CR ₁ CONR ₂ R ₃ (wherein, R ₁ represents H or an alkyl group, and R ₂ ,
R ₃ is H or hydroxyl, epoxy, cyano,
Alkyl, allyl, substituted or unsubstituted with halogen, carbonyl, isocyano, nitro, alkoxyl, allyloxyl, aryloxyl, thiocarbonyl, dithiocarboxyl group, etc.
Also useful are acrylamide and methacrylamide represented by aryl, alkenyl, etc. groups such as N-propylacrylamide, N-ethylmethacrylamide, N,N-ethyl, propylacrylamide, N,N-dimethylmethacrylamide, N- Examples include methylcarbonylbutyl methacrylamide. Furthermore, the general formula CH ₂ =CHOCOR ₁ (wherein, R ₁ is alkyl substituted with or unsubstituted with hydroxyl, amino, nitro, cyano, isocyano, carbonyl, halogen, epoxy, thiocarbonyl, dithiocarboxyl, alkanoyloxy group, etc.) , aryl, allyl, alkenyl, etc.), and the general formula CH ₂ = CR ₁ C ₆ H ₄ R ₂ (wherein, R ₁ is H or an alkyl group, and R ₂ is H
or hydroxyl, alkoxyl, alkenyloxy, carbalkoxyl, nitro, halogen,
It includes styrene and styrene derivatives represented by groups such as cyano, amino, isocyano, carbonyl, thiocarbonyl, dithiocarboxyl, or alkyl, allyl, aryl groups substituted or unsubstituted with these groups, It is not limited to these. Note that these vinyl monomers may be used alone or in combination of two or more. Furthermore, it may be used together with other vinyl monomers, but in that case, it is preferable to use the vinyl monomer as the main component. In addition to known chemical initiation methods, energy irradiation methods such as ultraviolet rays, gamma rays, and electron beams can be used as the graft polymerization method. Legal is practical. The graft polymerization weight increase rate greatly affects dyeability and should be at least 15% of the fiber weight, preferably 30 to 10%, but depending on the type of vinyl monomer used, it may not be possible to increase the weight by 70% or more. It is preferable to set it appropriately because the texture of the fiber changes and the color fastness may even decrease. In addition, graft polymerization can be carried out by impregnating protein fibers with a monomer-containing solution, or by applying an appropriate heating method such as dry heat, steam heating, micro-heating, etc. after attaching the monomer-containing solution to protein fibers. A method of wave heating treatment can also be used. The graft polymerization processing fluid contains surfactants to allow the processing fluid to penetrate quickly and smoothly into the fibers, additives to adjust the pH of the processing fluid, and other adjustments to adjust the viscosity of the processing fluid. Auxiliary agents such as adhesives, for example, thickeners, may be added as appropriate. The protein fibers to which the method of the present invention is applied may be thread-like, cloth-like, cotton-like, or paper-like, and can be applied alone or in blends or weaves of two or more types. Further, these fibers may be either unrefined or refined. The initiators used in the present invention include those known in the art, such as persulfates such as potassium, sodium and ammonium persulfates, inorganic and organic peroxides such as hydrogen peroxide, peracetic acid or benzoyl peroxide. , perborates, permanganates, etc., and these may be used alone or in combination, and reducing compounds such as sulfites, thiosulfates, and thiourea dioxide may be used in combination to achieve redox polymerization. You can also. When attaching a processing liquid containing a processing agent as described above to protein fibers, various methods can be used. For example, it may be immersed in the machining fluid and squeezed, or any suitable method may be used, such as spraying the machining fluid, patting, or rotating a roller whose lower part is immersed in the machining fluid and passing over it. is used. In addition, either a discontinuous type or a continuous type may be used.For cloth-like items, a continuous type may be used, for example, the cloth is immersed in the machining liquid while being guided by guide rolls installed in a tank containing the machining liquid. Productivity can be increased by stacking the liquid and finally squeezing it with a mangle, or by passing it over a pipe with many pores and removing the excess processing liquid by suctioning it under reduced pressure through the pores. can. In any case, it is necessary to operate the processing liquid so that it adheres to the protein fibers as uniformly as possible. When applying processing fluid, the amount of adhesion is 50 to 350% by weight, preferably 70 to 200% by weight, based on the protein fiber.
The weight% range is good, and the amount of monomer attached is 20 to 100% by weight, preferably 30 to 100% by weight based on the weight of the fiber.
It is preferably in the range of 80% by weight, and may be appropriately selected from within the above range depending on the type of protein fiber, the type of monomer, and the desired graft polymerization rate. Note that the present invention can of course be practiced even outside the above range. Dyes that can dye the modified protein fibers or structures containing protein fibers according to the invention also include CIDisperse Blue series, such as Blue 3, 58, 87, 95, 106, Yellow series, such as Yellow 3, 7. , 23, 54, 64, Orange series, e.g. Orange 1, 20, 21, Rad series, e.g. 11, 50,
60, Violet series, such as Violet 1, 28, 87, etc., but are not limited to these. Commercially available dry transfer printing dyes developed for polyester, dyes and transfer papers suitable for transfer paper and acrylic fibers can also be used. In view of the purpose of the present invention, known printing methods can be applied to dyeing, but the present invention is particularly useful when dyeing is performed using a sublimation transfer printing method, and dyeing can be carried out under pressure up to ~300 g/cm ² or without pressure. , which can be performed by heating up to ~250°C.
It is also possible to use the well-known Nao Printer 2F, Mail and Kanegisa, or to perform steaming after transfer printing. The present invention will be explained in more detail with reference to Examples below. Unless otherwise specified, percentages and parts shown in Examples are percentages and parts by weight, and various measured values were determined according to the following methods. Graft weight increase rate (%) = (Weight of graft polymerized fiber - Weight of unprocessed fiber) ÷ Weight of unprocessed fiber x 100 Dyeability is measured at 600 nm using a Hitachi UV-VIS photoelectric colorimeter.
The color fastness indicated by the magnitude (1 to 5 levels) of the surface dye density determined from the surface reflectance measured in 1 was evaluated according to the following JIS standards. That is, dry cleaning is L0860−1974, contamination is L0848−
1974D, friction is L0849−1971 (Gakushin type). Example 1 Scoured and bleached 16-momme silk habutae was soaked in a 1N sodium thiosulfate aqueous solution, squeezed to about 100% with a two-roll mangle, and then mixed with 20 parts of ethylene glycol diglycidyl ether and carbon tetrachloride. Processing liquid consisting of 70 parts and 10 parts of impropanol (common ratio approx. 20
2 times) and treated at 75-76°C for 3 hours. After treatment, it was washed with boiling acetone, soapy water, water, and dried. The weight increase rate due to this treatment is 17%
It was hot. This epoxy-treated silk cloth was placed in an aqueous emulsion (20 times the conventional ratio) containing 40% styrene, 3% nonionic emulsifier, 3% ammonium persulfate, and 0.04% formic acid based on the silk fiber, and the epoxy-treated silk fabric was heated to 85% for 30 minutes. After gradually raising the temperature to ℃, graft polymerization was performed at the same temperature for 30 minutes. After cooling to around room temperature, it was washed with water, further washed with soapy water at 50°C and warm water, and then air-dried to obtain graft polymerized silk fibers. After graft polymerization processing, the silk fibers were layered with transfer paper (blue) manufactured by Nippon Thermo Printex Co., Ltd., and transferred using a transfer printing machine (Neo Printer 2F model) manufactured by Naomoto Kogyo Co., Ltd.
Thermal transfer was performed at 230°C for 30 seconds. For comparison,
Comparative Example 1-1 is a case in which the dye was thermally transferred to the same silk habutae under the same conditions without epoxy compound treatment or graft polymerization treatment, and silk fiber was treated with an epoxy compound with resorcin diglycidyl ether and graft polymerization treatment was performed. Comparative Example 1-2 shows a case in which the dye was thermally transferred under the same conditions without treating the silk fiber with an epoxy compound, and Comparative Example 1-2 is a case in which the silk fiber was graft-polymerized with styrene in the same manner as above without being treated with an epoxy compound and the dye was thermally transferred in the same manner. 3. Comparative Examples 1-4 were cases in which polyester taffeta was transfer-dyed using the same dye and under the same conditions, and the results were as shown in Table 1, which summarizes the dyeability and color fastness of the dyes.

[Table] As is clear from the table above, if the silk fiber is used as it is, as in Comparative Example 1-1, it will hardly be dyed, and even if it is treated only with an epoxy compound (Comparative Example 1-2), the dyeing will not be sufficient. be. In Comparative Example 1-3, which was only subjected to graft polymerization, the dyeing was sufficient, but the color fastness was poor. On the other hand, Example 1, which was graft-polymerized after being treated with an epoxy compound, showed high dyeing properties equivalent to those of the polyester of Comparative Examples 1-4, and had sufficiently practical dry cleaning resistance and abrasion resistance. degree. In particular, in the case of Example 1, the color of the transfer paper also faded as in Comparative Examples 1-4 of the polyester fabric, indicating that the vapor phase diffusion of the dye occurred easily. On the other hand, Comparative Examples 1-1, 1-2, 1
-3, it is known that the degree of fading of the transfer paper is poor and the diffusion is insufficient. Example 2 Scoured silk thread (21 medium/2 pairs) impregnated with 98% of 10% potassium thiocyanate aqueous solution was mixed with 15 parts of resorcin diglycidyl ether, 60 parts of perchlorethylene,
It was immersed in a processing solution consisting of 10 parts of ethanol and 15 parts of n-hexane (about 15 times the standard ratio) and treated at 70 to 75°C for 3 hours. After the treatment, the same treatment as in Example 1 was carried out, and the amount added was 12%. The epoxy-treated silk thread was added to an aqueous emulsion (20 times the common ratio) containing 35% ethoxyethyl methacrylate, 5% hydroxyethyl acrylate, 3% nonionic emulsifier, 3% benzoyl peroxide, and 0.06% formic acid based on the fiber. and 30
The temperature was increased to 80° C. for 45 minutes and 85° C. for 45 minutes, and after further treatment at this temperature for 15 minutes, the same treatment as in Example 1 was carried out. The graft polymerized yarn was made into a woven fabric, and then thermally transferred using the same dye transfer paper as in Example 1. The results are shown in Table 1, and the woven fabric had good dyeability and practical fastness comparable to those of Example 1. Example 3 10 parts of vinyl cyclohexene dioxide, 10 parts of phenyl glycidyl ether, 1.3 parts of a foaming agent consisting of an ethylene oxide adduct of a long-chain alcohol, n
- 5 parts octane, polyethylene oxide stabilizer
A treatment solution prepared by adding an aqueous potassium bromide solution to a concentration of 1N to 0.5 parts of a nonionic surfactant, 15 parts of a nonionic surfactant, and 0.2 parts of a silicone wetting agent was foamed in a commercially available Oakes mixer. The foam composition was applied to a scouring and bleached 16 monme silk habutae using an applicator, compressed and impregnated to 150%, sealed in a glass container as it was, and placed in a 2450 MHz box oven.
Microwave treatment was performed at 600W for 3 minutes. Thereafter, when it was treated in the same manner as in Example 1, the addition rate was 9%. 10% methacrylamide for the fiber;
N,N-di-n-butyl methacrylamide 30%,
3% nonionic emulsifier, 30% hydrogen peroxide 8%,
In an aqueous emulsion containing 0.05% concentrated sulfuric acid (20 times the standard ratio),
The epoxy-treated cloth was placed and treated in the same manner as in Example 2, and then thermal transfer was performed in the same manner as in Example 1 using the same dye transfer paper. The results are shown in Table 1. Comparing the results in the same table, although there are some differences in dyeability due to differences in hydrophobicity of the graft-polymerized vinyl monomer, dry cleaning resistance is comparable to that of the polyester taffeta of Comparative Example 1-4. Demonstrates abrasion resistance. Example 4 10 parts of glycerin triglycidyl ether, 10 parts of phenyl glycidyl ether, trichloroethane
When Eri silkworm cloth was treated under the same conditions as in Example 1 using an epoxy processing liquid consisting of 60 parts, butanol, 10 parts, and 10 parts of decalin, and a 1N aqueous sodium acetate solution, the amount added was 11%. Ta. After treating the epoxy-treated fabric in the same manner as in Example 1 using the same graft polymerization solution as in Example 1 in which 35% butyl methacrylate and 5% hexyl acrylate were added instead of styrene to the treated fabric. ,
Thermal transfer was performed under the same conditions as in Example 1 using transfer paper (red) manufactured by Nippon Thermo Printex Co., Ltd.
Furthermore, the same dyeability and color fastness tests as in Example 1 were conducted and the results are shown in Table 2. For comparison, Comparative Example 4-1 is a case in which the same silkworm fabric is heat-transferred with the same dye without both treatments; Comparative Example 4-2 is a case in which only an epoxy compound is heat-transfer-dyed; and Comparative Example 4-2 is a case in which dyeing is performed after only graft polymerization processing Comparative Example 4-3 is shown in the same table as Comparative Example 4-3, and polyester taffeta dyed under the same conditions without being processed.

[Table] As is clear from Table 2, the silk woven fabric as it is is hardly dyed as in Comparative Example 4-1. Even with the epoxy compound treatment (Comparative Example 4-2), the dyeing was insufficient. In Comparative Example 4-3, which was only subjected to graft polymerization, the dyeing was relatively good, but the color fastness was poor. On the other hand, Example 4 is printed in a deep color and has practical performance equivalent to polyester in terms of dry cleaning resistance and abrasion fastness. Even though the dye was different from Example 1, the fading of the transfer paper in Example 4 was the same as in Comparative Example 4-4.
It can be seen that vapor phase diffusion of the dye occurs easily. On the other hand, Comparative Examples 4-1, 4-2, 4-3
It is known that the degree of color fading of the transfer paper is also poor and the diffusion is insufficient. Example 5 Propylene glycol diglycidyl ether 20
part, 10 parts of hydrogenated bisphenol A diglycidyl ether, 3 parts of toluene, and a chain-like secondary compound having 11 to 15 carbon atoms.
1 part of a spray stabilizer consisting of an ethylene oxide adduct of alcohol, 15 parts of an emulsion containing low molecular weight polyethylene and a nonionic surfactant at a concentration of
A treatment solution to which an aqueous sodium nitrate solution was added to give a concentration of 0.8N was sprayed using a commercially available nozzle vibrating sprayer. Applying the mist composition to a scoured rabbit blanket,
Press impregnated to 160%. Thereafter, the same treatment as in Example 3 was carried out. The amount added was 15%. The epoxy-treated fabric was treated in the same manner as in Example 2 in the same treatment solution as in Example 2, using 35 parts of benzyl methacrylate and 5 parts of butyl acrylate in place of ethoxyethyl methacrylate and hydroxyacrylate. Processed. Next, thermal transfer was performed in the same manner as in Example 4 using the same dye transfer paper. As shown in Table 2, good dyeability and sufficient fastness were obtained. Example 6 Propylene glycol diglycidyl ether 20
When a mohair cloth was processed in the same manner as in Example 2 using the same treatment solution as in Example 2 except that 1 part and 5 parts of glycerin triglycidyl ether were used in place of resorcin diglycidyl ether, the amount added was 16%. Ta. 20 parts of p-bromostyrene for the fabric;
10 parts styrene, 10 parts butoxyethyl methacrylate
The epoxy compound-treated fabric was treated with the same treatment solution as in Example 1 using styrene instead of
processed in the same way. Next, thermal transfer was performed in the same manner as in Example 4 using the same dye transfer paper. Good dyeability and sufficient fastness as shown in Table 2 were obtained. Example 7 Aqueous emulsion consisting of 5 parts of N,N-diglycidylaniline, 15 parts of ethylene glycol diglycidyl ether, 0.2 parts of a nonionic surfactant, and an aqueous potassium chloride solution added to a concentration of 0.8N. Wool muslin was immersed in the solution at a concentration 20 times that of ordinary wool, and kept at 70°C for 3 hours. Thereafter, the same treatment as in Example 1 was carried out to obtain a treated cloth with an addition amount of 13%. The epoxy-treated fabric was treated in the same treatment solution as in Example 1 under the same conditions as in Example 1, using 35 parts of p-methylstyrene and 5 parts of butoxyethyl acrylate in place of styrene. . Then, thermal transfer was performed in the same manner using dye transfer paper containing CIDisperse Blue 3, and the test results are shown in Table 3. In addition, Comparative Example 7, in which a sample was printed without both processing
-1. Comparative example 7, printed only with epoxy treatment -
2. Comparative example 7-, printed only by graft polymerization processing
3. Comparative example 7-4 of printing polyester taffeta
Also shown in Table 3. Example 7 showed the same disperse dye dyeing rate and color fastness as Comparative Example 7-4, which printed polyester taffeta, but Comparative Example 7-2, which was treated only with an epoxy compound, had insufficient dyeing amount. Comparative Example 7-3, which was only subjected to graft polymerization, had poor dye fastness, and both were poor in practicality.

[Table] Example 8 50/50 polyester/wool blend serge
Immerse in 0.3N lithium thiocyanide aqueous solution,
After squeezing to 100%, add 5 parts of epichlorohydrin,
Vinyl cyclohexane oxide 5 parts, styrene oxide 10 parts, perchlorethylene 40 parts, hexane
The sample was immersed in a processing solution consisting of 20 parts of 20 parts, 10 parts of butanol, and 10 parts of methanol at 15 times the standard ratio, heated at 75°C for 2 hours, and treated in the same manner as in Example 1. Addition amount is 12
It was %. 30 parts of octical methacrylate, 10 parts of phenoxyethyl methacrylate for the cloth
The epoxy-treated fabric was treated in the same manner as in Example 1 using the same processing liquid as in Example 1 except that styrene was used instead of styrene. Next, thermal transfer was performed using the same transfer paper as in Example 7 under the same conditions. Comparative Example 8-1 is a case in which the same serge was printed without any processing.
Comparative Example 8 - Printing with only epoxy treatment
2. Comparative Example 8-3 was a case in which printing was performed only by graft polymerization. The results are also listed in Table 3.
Comparative Example 8-2, which was treated only with an epoxy compound, was also dyed in a considerably deep color, but in Example 8, which was subjected to graft polymerization, the dyeing property was further improved. Moreover, in Comparative Example 8-3, in which only graft polymerization was performed, the dyeing was deep, but the fastness was insufficient. Note that Comparative Example 7-4 is Comparative Example 8- of Example 8.
It can also be considered as 4. As is clear from examining the Examples and Comparative Examples above, even when protein fibers are subjected to graft polymerization processing with a large amount of highly hydrophobic polymerizable organic monomers and are printed and dyed, the substrate is not strongly dyed. Therefore, in view of the fact that the color fastness is low and it tends to become uneven, the present invention provides wrinkle resistance, shrink resistance, light fastness, and chemical resistance by treating the fiber with an epoxy compound. , reduce the hydrophilicity of protein fibers to improve printing color fastness and setting properties, and then perform graft polymerization to further improve dyeing properties.
This resulted in further improvements in print adhesion and color fastness. Therefore, according to the present invention, protein fibers and structures such as fabrics containing protein fibers are sublimated and vapor-phase dyed using disperse dyes to achieve dyeing properties and color fastness equivalent to highly hydrophobic synthetic fibers such as polyester. It has characteristics that contribute to the expansion of applications. Effects of the Invention As described above, in the present invention, a protein fiber structure or a protein fiber-containing structure is first treated with an epoxy compound, and the functional amino acid residues are hydroxyalkylated to uniformly achieve appropriate hydrophobicity. be given to At that time, wrinkle resistance, light resistance, chemical resistance, etc. are permanently imparted without impairing the characteristics of the protein fiber. Then, when a hydrophobic vinyl monomer is grafted, the graft polymer is deposited within the fiber much more uniformly than when no epoxy compound treatment is performed, so the grafting efficiency is greatly increased and a large amount of It is confirmed that even when the vinyl monomer is graft-polymerized, the physical properties of the graft-polymerized fiber structure do not deteriorate, nor does it change in color or become brittle due to changes over time. Therefore, it is possible to obtain a protein fiber structure or a protein fiber-containing structure which not only is dyed with a disperse dye in a deep and strong transfer print, but also has significantly improved chargeability and light resistance.

Claims (1)

[Scope of Claims] 1 Disperse dye-dyable protein fibers and protein fibers are characterized in that protein fibers and structures containing protein fibers are treated with an epoxy compound and then graft-polymerized with a hydrophobic vinyl compound. Containing structures. 2. Disperse dyeable protein fibers obtained by treatment with an epoxy compound and then graft polymerization with a hydrophobic vinyl compound and structures containing the protein fibers are treated with disperse dyes, oil-soluble dyes, basic dyes, benzene, etc. A method for printing protein fibers and structures containing protein fibers, the method comprising printing using at least one dye selected from the group consisting of soluble dyes, mordant dyes, and vat dyes. 3 The protein fibers mentioned above are domestic silkworms, natural silkworms, Eri silkworms,
The printing method according to claim 2, which is made of silk fibers such as citrus silkworm. 4. The printing method according to claim 2, wherein the protein fiber is an animal hair fiber such as wool, cashmere, mohair, or rabbit hair. 5 The above epoxy compound has the general formula (However, in the formula, R ₁ , R ₂ , R ₃ , and R ₄ are hydrogen atoms or arbitrary organic residues that allow the compound of the formula to exist stably and do not interfere with the reaction with protein fibers, and are interconnected to form a ring. The textile printing method according to any one of claims 2 to 4, wherein the printing method is at least one compound represented by: 6 The above organic residue is nitro, nitroso, cyano,
isocyano, halogen, carbonyl, carboxyl, thiocarbonyl, dithiocarboxyl, hydroxyl, amino, amido, alkoxyl, epoxy, sulfonyl, sulfanyl, imino, imido, phosphonyl, phosphinyl groups, and alkyl substituted or unsubstituted for these groups; The printing method according to claim 5, wherein the printing method is selected from the group consisting of alkenyl, alkynyl, aralkyl, aryl, alkoxyl, aryloxy, allyl, and allyloxy groups. 7. A patent claim in which the treatment with the epoxy compound is carried out in the coexistence of an aqueous solution or an aqueous solution of one or more neutral salts or weakly basic salts of metals selected from alkali metals or alkaline earth metals. The textile printing method according to any one of the ranges 2 to 6. 8 The treatment with the epoxy compound impregnates the structure with the epoxy compound or a liquid, mist, or foam composition containing the epoxy compound,
The textile printing method according to any one of claims 2 to 7, which is carried out by dry heat, steam or microwave treatment without pre-drying. 9 The above vinyl compound has the general formula CH ₂ = CR ₁ C ₆ H ₄ R ₂ (wherein, R ₁ is H or an alkyl group, and R ₂ is H or alkoxyl, epoxy, carbalkoxyl, alkenyloxy, nitro, Alkyl, alkenyl, alkynyl, aralkyl, aryl, alkoxy, aryloxy, allyl, allyloxy, alkanoyloxy, substituted or unsubstituted with groups such as halogen, cyano, isocyano, amino, carbonyl, hydroxyl, dithiocarboxyl, thiocarbonyl, etc. The textile printing method according to any one of claims 2 to 8, comprising one or more styrene derivatives represented by the following groups. 10 The above vinyl compound has the general formula CH ₂ = CR ₁ CO ₂ R ₂ (wherein, R ₁ represents H, halogen, or an alkyl group, and R ₂ represents hydroxyl, amino, alkoxyl, epoxy, halogen, carbonyl, or carbonyl group). Alkoxyl, alkenyloxyl, nitro,
Acrylic acid and methacrylic acid esters represented by alkyl, alkenyl, alkynyl, aralkyl, aryl, allyl, etc., substituted or unsubstituted with groups such as cyano, isocyano, thiocarbonyl, dithiocarboxyl, alkanoyloxyl, etc. Claims 2 to 8 consist of one or more types selected from
The printing method described in any one of the paragraphs. 11 The above vinyl compound has the general formula CH ₂ =CHOCOR ₁ (wherein R ₁ is substituted with a group such as hydroxyl, amino, cyano, isocyano, nitro, halogen, epoxy, carbonyl, thiocarbonyl, dithiocarboxyl, alkanoyloxy, etc.) (substituted or unsubstituted alkyl, allyl, aryl, alkenyl, alkynyl, etc.)
The textile printing method according to any one of claims 2 to 8, comprising one or more types selected from vinyl alcohol derivatives represented by the following. 12 The above vinyl compound has the general formula CH ₂ = CR ₁ CONR ₂ R ₃ (wherein, R ₁ represents H or an alkyl group,
R ₂ and R ₃ are H or alkyl, allyl, aryl substituted or unsubstituted with groups such as hydroxyl, epoxy, cyano, isocyano, nitro, halogen, carbonyl, thiocarbonyl, dithiocarboxyl, alkoxyl, allyloxyl, aryloxyl, etc. The textile printing method according to any one of claims 2 to 8, comprising one or more selected from acrylamide and methacrylamide represented by groups such as , alkenyl, etc. 13 The above vinyl compound is from a compound represented by CH ₂ = CR ₁ C ₆ H ₄ R ₂ , CH ₂ = CR ₁ CO ₂ R ₂ , CH ₂ = CHOCOR ₁ and CH ₂ = CR ₁ CONR ₂ R ₃ At least one compound selected from the group consisting of:
The printing method according to any one of Section 8. 14. The textile printing method according to claims 2 to 13, wherein the graft polymerization is carried out in a deoxidizing system. 15. The textile printing method according to any one of claims 2 to 13, wherein the graft polymerization is carried out by impregnating the structure with an aqueous solution or dispersion of a vinyl compound. 16. The textile printing method according to any one of claims 2 to 15, wherein the graft polymerization is carried out using a polymerization catalyst or by energy irradiation. 17 Graft polymerization is carried out by impregnating the above structure with a vinyl compound or a liquid, mist, or foam composition containing a vinyl compound and subjecting it to dry heat, steam, or microwave treatment without pre-drying. Claims 2 to 1
The printing method described in any one of Section 6. 18. The textile printing method according to any one of claims 2 to 17, wherein the textile printing method is a sublimation transfer textile printing method.