JPS62250275A - Modification of protein fiber and protein fiber-containing structure - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for processing protein fibers such as silk and wool, and more particularly to protein fibers in the form of cloth, thread, cotton, paper, and powder, and structures containing the same. The present invention relates to a chemical modification processing method that imparts excellent dyeing properties, antistatic properties, light fastness, anti-wrinkle properties, bulkiness, pleatability, etc. 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.

Conventional technology Although protein fibers such as silk and wool have an elegant luster and are excellent in flexibility, moisture absorption, and dyeability, they have poor wrinkle resistance, shrink resistance, light resistance, pleatability, etc. Various methods have been proposed, such as resin processing methods using melamine-formalin resin, urea-formalin resin, epoxy resin, etc., methods of processing with tin chloride or tannic acid, and more recently, methods using various vinyl compounds. There are processing methods such as graft polymerization.

Problems to be Solved by the Invention Graft polymerization of a suitable amount of a vinyl compound onto protein fibers such as silk and wool is particularly welcomed in the silk dyeing industry because it increases elasticity and bulk. However, although there are differences in degree depending on the type of vinyl compound,
In conventional graft polymerization, the elegant luster and soft texture inherent in protein fibers such as silk and wool tend to be lost, and especially when hydrophobic monomers such as styrene, methyl methacrylate, and acrylonitrile are grafted, the graft polymer In addition to being prone to uneven processing because it is difficult to deposit uniformly within the fiber, it also reduces dyeability and hygroscopicity, or increases flammability. Grafted protein fibers had the problem of lacking bulk and giving a hard texture. On the other hand, by adding an epoxy compound to the protein fibers, it became resistant to light, chemicals, and shrink-proof.

A method was developed that could provide wrinkle resistance (Special Publication Publication No. 47-2
4199.52-38131), but lacks bulk and does not significantly improve abrasion resistance.6 The present inventors have conducted intensive research to solve the above problems, and have found that it has excellent gloss, flexibility, and dyeability. , and has completed a manufacturing method for protein fiber structures and structures containing protein fibers made of silk or wool, which have excellent antistatic properties, white skin, wrinkle resistance, light resistance, bulkiness, pleatability, and abrasion resistance. It is something.

A means for solving the problems, that is, the present invention, is to treat protein fiber structures and structures containing protein fibers with various epoxy compounds in the presence of a neutral salt aqueous solution, and then graft vinyl monomers. Characterized by polymerization.

When an epoxy compound is added to protein fibers and structures containing protein fibers to block amino groups, carboxyl groups, alcoholic and phenolic hydroxyl groups in the fibers,
Light resistance, chemical resistance, and antistatic properties without any change in dyeing properties and hygroscopicity.

It is known that wrinkle resistance etc. are improved. However, it is difficult to improve the abrasion resistance, dry wrinkle resistance, and bulkiness to the same level as synthetic fibers or structures containing synthetic fibers. However, when a vinyl compound is further graft-polymerized to a protein fiber structure or a structure containing protein fibers treated with an epoxy compound, 10 to 15%
Even at a moderate graft polymerization weight increase rate, the abrasion resistance, dry wrinkle resistance, and bulkiness are further improved. Furthermore, when graft polymerized in large amounts, bulkiness is poor and hydroxyethyl methacrylate gives a hard texture (Japanese Patent Publication No. 57-15
228) also provides a texture that is as bulky and flexible as polyethylene glycol monomethacrylate and polypropylene glycol monomethacrylate (Japanese Patent Publication No. 57-13665). Furthermore, acrylamide and methacrylamide (described in Japanese Patent Publication No. 15231/1983), which conventionally tended to cause discoloration and embrittlement during post-processing and product use when graft polymerized in large quantities, also contain protein fiber structures or protein fibers as in the present invention. It has been found that treating the structure with an epoxy compound followed by graft polymerization provides a fabricated structure as good as N-alkyl or N,N-dialkyl acrylates or methacrylates. In other words, the addition of an epoxy compound gives protein fibers the above-mentioned performance improvements, and the increased hydrophobicity increases the affinity for vinyl compounds, allowing even hydrophobic vinyl compounds to diffuse uniformly and quickly within the fibers. become. In addition, since the increase in substituted hydroxyethyl groups caused by the addition of an epoxy compound is accompanied by a uniform increase in the number of graft polymers deposited, the combination of treatment with an epoxy compound and graft polymerization treatment with a vinyl compound can be used in combination with treatment with an epoxy compound and graft polymerization treatment with a vinyl compound. It is thought that an unexpected synergistic effect was exerted. By the way, if the order of the two treatments is reversed, that is, graft polymerization with a vinyl compound is performed first, and then treatment with an epoxy compound is performed,
Although the advantages of each treatment were obtained, the disadvantages remained unimproved. In other words, even if a hydrophobic monomer such as styrene is first graft-polymerized and then treated with an epoxy compound, its affinity with protein fibers is poor, resulting in uneven graft polymerization and the resulting dyeability and The uneven staining and the like are not much improved, so the order of the processing steps in the present invention is essential, and only then will the synergistic effect of the two steps appear.

The protein fibers of the present invention include silks from domestic silkworms, Eri silkworms, natural silkworms, and Japanese cypress silkworms, as well as animal hair fibers such as wool, mohair, cashmere, rabbit hair, and wool, and processes such as spinning or burning into secondary silk threads and raw silk. Refined yarn, that is, all types of fibers such as spun, twisted, sewing, knitting, and non-woven yarns, as well as structures that contain some or all of them.

A known method (Japanese Patent Publication No. 47-24199.52-38131) can be used for the treatment with an epoxy compound in the present invention. 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. According to
Processing with epoxy compounds can be carried out without sacrificing the advantages of the structure.

Catalysts for treating epoxy compounds used in the present invention are known catalysts, such as alkali metals such as lithium, sodium, potassium, rubidium, and osmium;
cations of alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium;
Fluorine, base, bromine, iodine, nitric acid, sulfuric acid, acetic acid, propionic acid.

A water-soluble neutral salt or weakly basic salt consisting of an anion such as sulfite, thiocyanate, thiosulfate, etc., and preferably has a pH of 1N aqueous solution 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 the salt concentration 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. In general, when soft fibers such as wool and rabbit hair are included, 0.1 to 0.
5 normal, preferably in the range of 0.5 to 1.5 normal in the case of silk fiber.

The epoxide that can be used in the present invention has the general formula (wherein R+, Rz, Rz, and Ra are hydrogen atoms or any organic residue that allows the compound of the formula to exist stably and does not interfere with the reaction with protein fibers). A group that can be linked together to form a ring.

These organic residues include nitro, nitroso, cyano, isocyano, halogen, carboxyl, dithiocarboxyl, carbonyl, thiocarbonyl, hydroxyl, amino, amido, alkoxyl, epoxy, sulfonyl, sulfanyl, imino, imide, phosphonyl, phosphinyl group, These groups are substituted or unsubstituted alkyl, alkenyl, alkynyl, aralkyl, aryl, alkoxyl, aryloxyl, allyl, allyloxyl, etc.). They include alkylene oxides, glycidyl ethers, glycidyl esters, epoxy acids and their esters and amides,
Included are glycidyl urethanes, glycidyl esters of sulfonic acid and phosphoric acid, epoxysilanes, epoxy alcohols, epoxy amines, halogenated epoxy L carbonyl epoxides, and the like.

Furthermore, since the epoxy compound treatment method is carried out in the presence of the above-mentioned neutral or weakly basic salt aqueous solution, the protein fibers are sufficiently swollen, and as a result, the above-mentioned epoxy compound diffuses uniformly and quickly into the protein fiber structure. Since it is carried out in
The reaction proceeds uniformly. Therefore, unlike the method of treatment with carboxylic acid anhydride or chloride (Japanese Patent Publication No. 57-30185), long-chain compounds are not inappropriate.These epoxy compounds can be used alone or in combination of two or more. However, considering the number of epoxy groups in the epoxy compound molecule, reactivity, and interaction of the epoxy compound,
In addition, it is important to select appropriate treatment conditions to suit the type and use of processed protein fibers and to determine appropriate reaction conditions. Such epoxy compounds can be used as is, but
It may be dissolved in a suitable catalyst, that is, if it is water-soluble, it can be used as is, 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 epoxy compound as well as the type of protein fiber (fiber type, tissue, etc.), but is 2 to 30%, preferably 6 to 20%, based on the weight of the protein fiber.

Note that the treatment step using an epoxy compound in the present invention is as follows:
As known in the art (impregnating protein fibers in a formulation containing an epoxy compound, or incorporating a spray or foaming composition containing an epoxy compound into the protein fibers and heat-treating them. After drying, dry heat treatment is performed. All known heating methods such as steam treatment and microwave irradiation treatment can be applied to other heating methods.

The protein fiber structure or protein fiber-containing structure treated with the epoxy compound in this manner is soaped and washed with water according to a conventional method, and then subjected to the next graft polymerization processing step as it is or after drying. In addition, if you use an aqueous solution that dyes protein fibers and does not decolorize in the next graft polymerization process and does not cause any problems during various post-processing processes, it can be used to dye protein fibers (permanently dye protein fibers). In addition to modification, dyeing can also be carried out at the same time (Special Publication No. 4B-22874, 49-3470)
.

For graft polymerization of protein fiber structures and structures containing protein fibers treated with epoxy compounds,
All known organic monomers that graft polymerize to protein fibers can be used. Among these, useful ones include the general formula % (where R represents H or halogen or an alkyl group, and R2 represents hydroxyl, amino, amide, alkoxyl, epoxy, imino, halogen, carbonyl, thiocarbonyl, carboxyl). acrylic acid and methacrylic acid ester derivatives represented by alkoxy, alkenyl, alkynyl, aralkyl, aryl, allyl, etc., substituted or unsubstituted with dithiocarboxyl, siahiisocyahanitro groups, etc. Acids and 2-chloroacrylic acid/methacrylic acid methyl, ethyl, propyl/butyl, allyl, vinyl, pendel, phenyl-glycidyl, tetrahydrofurfuryl,
Examples include hydroxyethyl, hydroxyermityl, ethoxypropyl/methoxybutyl, ethylene glycol, and propylene glycol ester.

Also, the general formula % formula % (wherein, R1 represents H or an alkyl group, and R3
is H or hydroxyl, epoxy, cyano, imino, imide, isocyano, carbonyl, dithiocarboxyl,
Also useful are acrylamide and methacrylamide represented by alkyl, aryl, allyl, alkenyl, etc., substituted or unsubstituted with carboxyl, thiocarbonyl, alkoxyl, allyloxyl, aryloxyl, etc., and N-propylacrylamide, N-ethylmethacrylamide, N,N-ethyl, propylacrylamide, N,N-dimethylmethacrylamide, N-
Examples include methylcarbonylbutyl methacrylamide.

Furthermore, the general formula % formula % (wherein R+ is substituted or unsubstituted with a group such as hydroxy, amino, amido, cyano, isocyano, nitro, halogen, epoxy, imino, carbonyl, thiocarbonyl, carboxyl, dithiocarboxyl, etc.) Alkyl, aryl.

esters of vinyl alcohol represented by (allyl, alkenyl, etc.) and the general formula GHz = CRI
C & H, R1 (wherein R1 is H or an alkyl group, R2 is H or a group such as hydroxyl, alkoxyl, alkenyloxy, carbalkoxyl, nitro, halogen, siahiisosiahamihaamide, thiocarbonyl, dithiocarboxyl, or substituted or unsubstituted alkyl, allyl, aryl, alkenyl, alkynyl, aralkyl, alkoxyl, aryloxy,
It includes styrene and styrene derivatives represented by allyloxy, alkanoyloxyl, etc.
It is not limited to these.

In addition, these vinyl monomers may be used alone or in combination of two or more types, or may be used together with other vinyl monomers, but in that case, the vinyl monomers mentioned above may be used in combination. It is preferable to mix and use them so that they form the main components.

As the graft polymerization method, in addition to known chemical initiation methods, energy irradiation methods such as ultraviolet rays, T-rays, and electron beams can be used. is practical. Graft polymerization weight increase rate greatly influences various physical properties, and at least 1% of the fiber weight
5% or more, preferably 30 to 100% is required,
Depending on the type of vinyl monomer used, increasing the amount by more than 70% may change the texture of the fibers and may even decrease physical properties, so it is preferable to determine the amount appropriately depending on the use of the structure. .

Graft polymerization processing can be carried out by impregnating protein fibers with a monomer-containing solution, or by applying an appropriate heating method such as dry heat, steaming, or microwave after adhering the monomer-containing solution to protein fibers. A method of heat treatment can also be used.

The graft polymerization processing liquid contains surfactants and pH of the processing liquid to allow the processing liquid to penetrate quickly and smoothly into the fibers.
Additives for adjusting the viscosity of the low processing fluid, adjusting agents for adjusting the viscosity of the low processing liquid, and various auxiliary agents such as sizing agents may be added as appropriate.

Protein fibers to which the method of the present invention is applied include thread-like, cloth-like,
It may be cotton-like or paper-like, and can be applied singly or as a blend or mixed fiber 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. , perborate, permanganate, etc. ・One or more types of these may be used. ・Furthermore, reducing compounds such as sulfite, 100sulfate, and thiourea dioxide may be used in combination with these. , redox polymerization can also be used.

When attaching a processing liquid containing a processing agent as described above to protein fibers, various methods can be used.For example, seeds may be soaked in the processing liquid and squeezed, or the processing liquid may be sprayed, An appropriate method may be used, such as patting or rotating a roller whose lower part is soaked in a machining fluid and passing over it. 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, a cloth is guided by guide rolls provided in a tank containing a machining liquid, and the seeds are soaked in the machining liquid. Finally, productivity can be increased by squeezing it with a mangle or by passing it through a pipe with many pores and removing the excess machining fluid by suctioning it under reduced pressure through the pores. 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 the processing fluid, the amount of adhesion is preferably in the range of 50 to 350% by weight, preferably 70 to 200% by weight based on the protein fiber, and the amount of graft monomer adhering is 10 to 350% by weight based on the weight of the fiber. ~100% by weight, preferably 30~
The range of 80% by weight is preferable, and it is preferable to appropriately select from within the above range depending on the type of protein fiber, the type of monomer, and the desired graft polymerization rate.Of course, the present invention can also be carried out even outside the above range. You can do it.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples. Note that the percentages and parts shown in the examples are weight percentages and parts by weight unless otherwise specified, and the processing and grafting weight increase rates (%) are [(
It was determined from the formula: processed fiber weight - unprocessed fiber weight, amount)/unprocessed fiber weight IXIQO.

@Mixing ratio (%) is expressed as the weight increase rate after drying the sample at 100℃ for 8 hours, weighing it accurately, and leaving it in a container at 20℃ and 65% relative humidity for 12 hours.・Frictional charging voltage (V) is , the sample is cotton cloth at 20°C.
Rotary static tester (at 65% relative humidity)
Measurements were made using a Kyoto University Kaken model manufactured by Koa Shokai.

The stainability was determined by the following method.

(a) Mix Ranil Yellow GO, 43 o 11 r%, Diazole Red 88 G, 23 owf%, Irgalan Brown 2 G L 1.9 ow N4, 2 g of soap
/J.

After adding 5 g/2 of Glauber's salt and dyeing at 90°C for 40 minutes at a bath ratio of 100 times, the reflectance (ρ) of the dyed fabric was measured using a self-recording spectrophotometer at a wavelength of 500 mμ (red) and 6
00-μ (blue), and /S was determined from the following formula.

K/S-(1-p)''/2p (b) The dyed product was visually judged, and the dyeing density of the unprocessed yarn was used as a standard of 100.

(c) The adsorption amount (%) of the dye was measured and evaluated.

Light resistance was measured using a weather meter (Toyo Rika-E-2) on the sample.
, 135 V, 16 A) for 300 hours, the reflectance of 425.550 and 650 mmμ (A, B, C, respectively) was measured using the above spectrophotometer using the magnesium oxide plate as a control. The yellowing index (Y) obtained from the following formula was used for evaluation.

y -100(C-a)/B Color fastness is dry cleaning L 0860-197
4. Friction L Tested according to 0849-1971.

Wrinkle resistance was evaluated by measuring the wrinkle recovery angle using the Sensant method.

Example 1 Scouring and bleaching 16 momme Habutae was soaked in an IN potassium thiocyanide aqueous solution, and the liquid was squeezed to about 90% with two mangles, and then 15 parts of ethylene glycol diglycidyl ether was added.
5 parts of phenyl glycidyl ether, 30 parts of carbon tetrachloride,
The seeds were soaked in a processing liquid (approximately 20 times the bath ratio) consisting of 40 parts of trichloroethane and 10 parts of isopropanol, and treated at TO-75°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 was 15%.

30% styrene, 10% hydroxyethyl methacrylate, 3% nonionic emulsifier, persulfuric acid 7. T: Aqueous emulsion containing 3% Yum and 0.17% formic acid?
The epoxy-treated silk fabric was placed in a bath (20 times the bath ratio), the temperature was gradually raised to 85° C. over 30 minutes, and then graft polymerization was performed at the same temperature for 30 minutes. After cooling to around room temperature, it was washed with water, then washed with soapy water at 50°C and warm water, and then air-dried to obtain a graft polymerized silk fabric. The texture and gloss of the processed fabric were almost the same as those of the original fabric before treatment, and it was also rich in bulk, and as shown in Table 1, it was also excellent in antistatic properties, light fastness, and dyeability.

For comparison, Comparative Example 1-1 uses the same silk habutae without reprocessing, Comparative Example 1-2 uses only epoxy treatment and no graft polymerization treatment, and Comparative Example 1-2 uses only graft polymerization treatment without epoxy treatment. Comparative Examples 1-3 are the cases in which this was applied, and their properties are summarized in Table 1. As is clear from the table, all of the physical property values of this example show excellent values that cannot be obtained by each individual processing alone, and it is thought that the combined processing of this example will produce an unexpected synergistic effect. It will be done.

Example 2 Refined silk thread (21 medium/2 pairs) impregnated with 100% 1% sodium thiosulfate aqueous solution was processed with 15 parts of resorcin diglycidyl ether, 60 parts of perchlorethylene, 15 parts of ethanol, and 10 parts of n-hexane. Liquid to bath ratio approx. 1
The seeds were soaked at a rate of 5 times and treated at 70-75°C for 3 hours.

After the treatment, the same process as in Example 1 was performed, and the amount added was 1.
It was 3%. Based on the fiber, 35% ethoxyethyl methacrylate, 5% methyl methacrylate, 3% nonionic emulsifier, 3% benzoyl peroxide, 0.06% concentrated sulfuric acid.
The epoxy-treated silk thread was placed in an aqueous emulsion (bath ratio: 20 times), heated to 80°C for 30 minutes, and further heated at this temperature for 20 minutes.
After processing for 1 minute, the same procedure as in Example 1 was carried out. The graft-polymerized yarn swelled more than twice as much, was extremely bulky, had a highly flexible texture, and had excellent weavability.

The light resistance and dyeability of the woven fabric were also excellent as shown in Table 1.

Example 3 10 parts of vinyl cyclohexene dioxide, 5 parts of phenyl glycidyl ether, 5 parts of ethyl glycidyl ether,
1.3 parts of a foaming agent consisting of an ethylene oxide adduct of a long-chain alcohol, 5 parts of n-octane, 0.5 parts of a polyethylene oxide stabilizer, 15 parts of a nonionic surfactant, and 0.2 parts of a silicone wetting agent. Then, a treatment solution to which an aqueous potassium bromide solution was added so as to have a concentration of IN was foamed in a commercially available Oakes type mixer. The foam composition was scoured and bleached.
Apply to Momome Fubutai using an applicator, squeeze to 150% impregnation, seal it in a glass container as it is, 245
It was placed in a 0MH2 open box and subjected to microwave treatment at 600 W for 3 minutes. Thereafter, when it was treated in the same manner as in Example 1, the addition rate was 9%. An aqueous emulsion containing 10% methacrylamide, 30% N,N-di-n-butylacrylamide, 3% nonionic emulsifier, 8% 30% hydrogen peroxide solution, and 0.1% formic acid based on the fibers. When the epoxy-treated cloth was placed in a solution (bath ratio 20%) and treated in the same manner as in Example 2, as shown in Table 1, in addition to flexibility, bulkiness, dyeability, and antistatic properties, it also had wrinkle resistance. An excellent processed cloth was obtained. In addition,
In an ignition test using a lighter, the flame-retardant properties were also confirmed, as the flame extinguished without burning out.

Example 4 15 parts of glycerin triglycidyl ether, 5 parts of styrene oxide, 60 parts of trichloroethane, 10 parts of butanol
and 10 parts of decalin;
When a citrus silkworm thread woven fabric was treated using the aqueous sodium acetate solution under the same conditions as in Example 1, the amount added was 11%. 10 parts of butyl acrylate for the processed fabric;
Using the same grafting solution as in Example 1 in which 30 parts of polyethylene glycol monomethacrylate was used instead of styrene and hydroxyethyl methacrylate,
When the epoxy treated cloth was treated in the same manner as in Example 1,
As shown in Table 2, a processed fabric with excellent bulkiness and antistatic properties and further improved wrinkle resistance was obtained. For comparison, the same table shows Comparative Example 4-1 in which neither treatment was performed on the same silkworm cloth, Comparative Example 4-2 in which only epoxy compound treatment was performed, and Comparative Example 4-3 in which only graft polymerization treatment was performed. In the staining test, erythrosin was used according to a conventional method.

As is clear from Table 2, epoxy treatment alone improved abrasion resistance and dyeability compared to untreated fabric, but there was no change in moisture absorption rate, and improvements in charging properties and wrinkle resistance were not significant. Although graft polymerization alone improves abrasion resistance and dyeability, the improvement in wrinkle resistance and bending resistance is small, and the hygroscopicity and chargeability are rather worsened. On the other hand, in this example, all physical property values were significantly improved, and these effects could not be expected from the results of each single processing treatment.

Example 5 10 parts of hydrogenated bisphenol A diglycidyl ether,
Propylene glycol diglycidyl ether 15 parts, 3
．． 5 parts of 4-epoxycyclohexylmethyl-3,4-engineered cyclohexane carboxylate, 3 parts of toluene, 1 part of a spray stabilizer consisting of an ethylene oxide adduct of a linear secondary alcohol having 11 to 15 carbon atoms, low molecular weight polyethylene and A treatment liquid prepared by adding an aqueous sodium nitrate solution to a concentration of 0.8N to 15 parts of an emulsion containing an ionic surfactant was sprayed using a commercially available nozzle vibrating sprayer.

The mist composition was applied to a scoured rabbit blanket and compressed to 160% impregnation. Thereafter, the same treatment as in Example 3 was carried out, and the amount added was 16%. 10 parts of benzyl methacrylate, 30 parts of butoxyethyl methacrylate based on the cloth
The epoxy-treated fabric was treated in the same manner as in Example 2 in the same treatment solution as in Example 2, using ethoxyethyl methacrylate and methyl methacrylate in place of ethoxyethyl methacrylate and methyl methacrylate. With a 1 t increase of 34%, felting did not occur, and a glossy, bulky, processed cloth with almost the same texture as unprocessed cloth and excellent light resistance and dyeability was obtained. The treated fabric and the raw fabric that was not reprocessed (Comparative Example 5-1) were 0. The solubility after soaking in an IN aqueous solution of caustic soda at 65° C. for 1 hour or in an IN aqueous hydrochloric acid solution for 1 hour was as shown in Table 3. Furthermore, Table 3 shows the dyeability (comparative example 5-1 is set as 100) and color fastness when dyeing with Mikasion Brilliant Blue R31.5% aqueous solution. Both were significantly improved compared to untreated cloth.

Example 6 15 parts of propylene glycol diglycidyl ether and 15 parts of glycerin triglycidyl ether were used in place of resorcinol diglycidyl ether, and the rest was as in Example 2.
When mohair cloth was processed in the same manner as in Example 2 using the same treatment solution, the amount added was 17%.

10 parts of p-bromostyrene, 3-chloro-
15 parts of 2-hydroxypropyl methacrylate, 15 parts of 2-hydroxy-3-phenoxypropyl methacrylate
The epoxy-treated fabric was treated in the same manner as in Example 1 using the same treatment solution as in Example 1 except that styrene and hydroxyethyl methacrylate were used in place of styrene and hydroxyethyl methacrylate. A glossy, bulky processed fabric with a texture almost the same as that of an unprocessed fabric was obtained, with an increase of 140% and no felting. The results of the alkali resistance and acid resistance tests similar to those in Example 5 and the dyeing tests using the same dyes as in Example 5 were also compared with the untreated fabric (Comparative Example 6-1) which was not reprocessed as shown in Table 3. It was very good.

Example 7 Aqueous milk 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. Add wool muslin to the suspension at a bath ratio of 2.
The seeds were soaked at 0x and treated at 70°C for 3 hours. Thereafter, the treatment was carried out in the same manner as in Example 1 to obtain a treated cloth with an addition amount of 13%. The epoxy-treated cloth was treated in the same treatment solution as in Example 1, using 30 parts of p-methylstyrene, 5 parts of butoxyethyl acrylate, and 5 parts of diethylene glycol methacrylate in place of styrene and hydroxyethyl methacrylate. The treatment was carried out under the same conditions as in Example 1.

Even when the weight was increased by 42%, felting did not occur, and a glossy and bulky fabric was obtained. The weight loss in the same alkali resistance and acid resistance tests as in Example 5 was as shown in Table 3. Table 3 also shows the dyeability with respect to the same dye as in Example 5 (comparative example 7-1 was set as 100). Comparative Example 7-1 is a sample that is not reprocessed, and Comparative Example 7-2 is a sample that is only treated with epoxy.
A sample subjected to only graft polymerization processing is also listed in Table 3 as Comparative Example 7-3.

As is clear from the same table, graft polymerization alone results in poor chemical resistance and uneven dyeing, which does not improve much, while epoxy treatment alone improves all properties, but is still insufficient for practical use. Met. However, as a result of combining the two treatments as in this example, very excellent properties were obtained, which appears to be due to a synergistic effect that could not be expected from the results of each treatment alone.

Example 8 Eri silk thread was soaked in a 0.8N aqueous solution of thiocyanated tum, and the solution was squeezed to 100%, followed by 10 parts of epichlorohydrin, 5 parts of bis(2,3-epoxy-6-methylcyclohexylmethyl) adipate, and polyethylene. 5 parts of glycol diglycidyl ether, 40 parts of perchlorethylene
parts, 20 parts of hexane, 10 parts of butanol, 1 part of methanol
The seeds were immersed in a processing solution consisting of 0 parts at a bath ratio of 15 times, and
The mixture was heated for 30 minutes and treated in the same manner as in Example 1.

The amount added was 16%.

The epoxy treatment system was treated in the same treatment solution as in Example 1 under the same conditions as in Example 1, using 30 parts of octyl methacrylate and 10 parts of phenoxyethyl methacrylate for the yarn in place of styrene and hydroxyethyl methacrylate. I processed it. The added amount was 37%, and a bulky processed yarn with gloss and good weavability was obtained.

Example 9 Polyester/wool blended serge of 50150 at 0°3
After soaking the seeds in a potassium thiocyanide aqueous solution of N and squeezing the liquid to 100%, the same epoxy compound processing liquid as in Example 6 was used to treat the same as in Example 6, and the following was also applied to Example 6.
A graft polymerization treatment was carried out in the same manner as above, and a glossy and bulky fabric was obtained without causing any felting. Chemical resistance, wrinkle resistance, moisture absorption, etc. were significantly superior to untreated cloth.

As is clear from examining the Examples and Comparative Examples above, when a vinyl compound is grafted onto protein fibers, the deposition of the graft polymer tends to be uneven and not uniform, and since no crosslinking has essentially occurred, it can be prevented. Wrinkle resistance, chemical resistance,
Light resistance etc. do not improve much. On the other hand, epoxy compound treatment causes crosslinking to occur uniformly, so although the above characteristics are improved, bulkiness is lacking and abrasion resistance does not improve much. However, according to the present invention (by performing graft polymerization processing after treatment with an epoxy compound, the properties that could not be improved by each of the above-mentioned single processing treatments could be improved on an unexpected synergistic scale).

Effects of the Invention As described above, in the present invention, a protein fiber structure or a structure containing protein fiber is first treated with an epoxy compound, and by substituting hydroxyethylation of the functional amino acid residues, it is made suitable for hydrophilic or hydrophobic properties. be applied uniformly. At this time, wrinkle resistance is achieved without sacrificing the characteristics of protein fibers.

When graft polymerization is performed with a vinyl compound that permanently imparts light resistance, chemical resistance, etc., the graft polymer is deposited much more uniformly within the fiber than when no epoxy compound treatment is applied. It was confirmed that the grafting efficiency was greatly increased, and even when a large amount of vinyl monomer was grafted, the physical properties of the grafted polymerized fiber structure did not deteriorate, nor did it become discolored or brittle due to changes over time. Ru.

Therefore, the protein fiber structure not only has improved bulk, abrasion resistance, and pleatability, but also has significantly improved antistatic properties, white skin, wrinkle resistance, light resistance, etc. without sacrificing its excellent gloss and flexibility. Alternatively, a structure containing protein fibers can be obtained.

Ganto Mochito Hatake Director of the Agency of Industrial Science and Technology Tatsu Todoroka (1 other person) Designated agent Director of the Textile and Polymer Materials Research Institute, Agency of Industrial Science and Technology Akihiro Ryotai Agent Shinji Kenbu (1 other person)

Claims (16)

[Claims] (1) A method for modifying protein fibers and structures containing protein fibers, which comprises treating protein fibers and structures containing protein fibers with an epoxy compound and then graft polymerizing them with a vinyl compound. (2) The modification method according to claim 1, wherein the protein fibers are silk fibers of domestic silkworms, natural silkworms, Eri silkworms, Japanese silkworms, and the like. (3) The modification method according to claim 1, wherein the protein fiber is an animal hair fiber such as wool, mohair, cashmere, or rabbit hair. (4) The above epoxy compound has a general formula ▲ mathematical formula, chemical formula, table, etc. Any one of claims 1 to 3, which is any organic residue that does not interfere, and which may be interconnected to form a ring. Modification method described in section. (5) The above organic residue is a nitro, nitroso, cyano, isocyano, halogen, carbonyl, thiocarbonyl, carboxyl, dithiocarboxyl, hydroxyl, amino, amido, alkoxyl, epoxy, sulfonyl, sulfanyl, imino, imido, phosphonyl, or phosphinyl group. and alkyl, alkenyl, alkynyl, aralkyl, aryl, alkoxyl, aryloxyl, allyl, and allyloxyl groups substituted or unsubstituted. Modification method. (6) A patent claim in which the treatment with an 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 a metal selected from alkali metals or alkaline earth metals. The modification method according to any one of the ranges 1 to 5. (7) The treatment with the epoxy compound involves impregnating the structure with the epoxy compound or a liquid, mist, or foam composition containing the epoxy compound, and then dry heat, steam, or microwave treatment without pre-drying. A reforming method according to any one of claims 1 to 6, which is carried out by: (8) The above vinyl compound has the general formula CH_2=CR_1C_6H_4R_2 (wherein, R_1 is H or an alkyl group, and R_2 is H
or groups such as hydroxyl, alkoxyl, carboalkoxyl, alkenyloxy, nitro, halogen, cyano, amino, amido, carbonyl, thiocarbonyl, dithiocarboxyl, or substituted or unsubstituted alkyl, allyl, aryl, alkenyl. , alkynyl, aralkyl, alkoxyl, aryloxyl, alkanoyloxyl, etc.) The modification method described in Section 1. (9) The above vinyl compound has the general formula CH_2=CR_1CO_2R_2 (wherein, R_1 represents H, halogen, or an alkyl group, and R_2 represents hydroxyl, amino, amide, alkoxyl, epoxy, imino, imide, halogen, carbonyl, or carboxyl group). , thiocarbonyl, dithiocarboxyl, alkanoyloxy, cyano, isocyano, nitro, etc., substituted or unsubstituted alkyl, alkenyl, alkynyl, aralkyl, aryl, allyl, etc.) acrylic acid and methacrylic acid The modification method according to any one of claims 1 to 7, comprising one or more ester derivatives selected from ester derivatives. (10) The above vinyl compound has the general formula CH_2=CHOCOR_1 (wherein R_1 is hydroxyl, amino, amide,
Vinyl alcohol derivatives represented by alkyl, aryl, allyl, alkenyl groups substituted or unsubstituted with groups such as cyano, isocyano, nitro, halogen, epoxy, imino, imido, carbonyl, thiocarbonyl, dithiocarboxyl, etc.) The modification method according to any one of claims 1 to 7, which comprises one or more selected from among these. (11) The above vinyl compound has the general formula CH_2=CR_1CONR_2R_3 (wherein, R_1 represents H or an alkyl group, and R_2
, R_3 is H or hydroxyl, epoxy, cyano, imino, imide, carboxyl, halogen, carbonyl,
selected from acrylamide and methacrylamide represented by alkyl, allyl, aryl, alkenyl, substituted or unsubstituted with groups such as thiocarbonyl, dithiocarboxyl, isocyano, alkoxyl, allyloxyl, aryloxyl, etc. 8. The method of modification according to any one of claims 1 to 7, which comprises one or more of the above. (12) The vinyl compound has the general formula CH_2=
At least one selected from the group consisting of compounds represented by CR_1C_6H_4R_2, CH_2=CR_1CO_2R_2, CH_2=CHOCOR_1 and CH_2=CR_1CONR_2R_3
The modification method according to any one of claims 1 to 7, which is a seed compound. (13) The modification method according to any one of claims 1 to 12, wherein the graft polymerization is performed in a deoxidizing system. (14) The modification method according to any one of claims 1 to 13, wherein the graft polymerization is carried out by impregnating the structure with an aqueous solution or dispersion of a vinyl compound. (15) Claims 1 to 1 in which the graft polymerization is carried out using a polymerization catalyst or by energy irradiation.
The modification method described in any one of Section 4. (16) 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. A method for modifying according to any one of claims 1 to 15.