JPS6223108B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for firmly dyeing modified synthetic fibers into which acidic groups have been introduced. While synthetic fibers have various excellent properties,
Compared to natural fibers, they generally lack hygroscopicity and antistatic properties, so they have the drawbacks of being uncomfortable when worn, easily getting dirty, and easily generating static electricity. Since polyamide fibers and polyacrylonitrile fibers are used in the field of underwear, there has been a particular desire for improvements in such properties. Conventionally, synthetic fibers are graft-polymerized with unsaturated organic acids, or acidic groups are introduced at the fiber manufacturing stage, and then alkali metal or
It is known that by substituting ammonia, it is possible to impart properties that synthetic fibers lack, such as antistatic properties, hygroscopic properties, and antifouling properties. However, conventionally known methods have disadvantages such as difficulty in dyeing, poor fastness even when dyed with excessive force, loss of quality, and lack of mass production. Specifically, for example, most of the dyes used for polyamide-based and modified polyamide-based fibers are acidic dyes, and as is well known, these acidic dyes cannot be dyed unless under acidic conditions. However, if polyamide fibers into which acidic groups have been introduced by methods such as graft polymerization with unsaturated organic acids are dyed with acidic dyes using known methods and then treated with alkali metals, the dyes will fall off rapidly, making color matching difficult. Have difficulty. Moreover, the wet fastness is poor and has no practical use. Furthermore, when dyeing is performed after alkali treatment, not only the color value does not improve, but also the color fastness such as light fastness and wet fastness decreases significantly, making it impractical. Against this background, the present invention aims to dye synthetic fibers into which acidic groups have been introduced in a durable manner. In order to achieve this object, the present invention has the following configuration. (1) Modification characterized by dyeing synthetic fibers into which 3.3×10 ^-6 gram equivalents/gram fiber or more of acidic groups or their salts have been introduced with a reactive dye in the presence of an acid. A method of dyeing synthetic fibers. (2) The method for dyeing modified synthetic fibers according to claim 1, wherein the reactive dye is selected from dichlortriazine dyes and fluorine-containing pyrimidine dyes. . (3) The method for dyeing modified synthetic fibers according to claim 1, wherein the dyeing treatment includes an alkali treatment step after the dyeing step with a reactive dye. (4) The method for dyeing modified synthetic fibers according to claim 3, wherein the alkali treatment is treatment with a quaternary ammonium salt. Even with this configuration, the modified synthetic fiber can be dyed firmly, and furthermore, by alkali treatment, the unique effect of allowing the hygroscopicity that it had before dyeing to be exhibited as it is, is achieved, but these will be explained in detail. do. That is, as described above, the present invention provides acidic groups or salts thereof in an amount of 3.3×10 ^-6 gram equivalent/gram.
By dyeing synthetic fibers that have been endowed with hydrophilic properties such as hygroscopicity by incorporating fibers with reactive dyes in the presence of acid, it is possible to obtain dyed products with extremely good color fastness. be. That is, in such modified synthetic fibers,
For example, even if polyamide fibers are dyed using conventionally known acid dyes, it is not possible to obtain a dyed product with good color fastness like ordinary polyamide. In particular, color fading when washed, wet fastness such as wet friction fastness, and dye transfer (water) fastness are extremely poor. Also, as a dyed seat,
Modified polyacrylic fibers copolymerized with a compound such as dimethylaminoethyl methacrylate can also be dyed with extremely good color fastness when dyed with a reactive dye in the presence of an acid. In this case, the use of conventionally known acid dyes results in dyeings with poor wet fastness, as in the case of modified polyamides. In addition, when dyeing with a reactive dye in the present invention, it is necessary to make the pH of the dye bath acidic, less than 7, preferably 6 or less, and if it is alkaline, as is the case when dyeing conventional cotton with a reactive dye, the dyeing will hardly be dyed. do not. As described above, when dyeing the modified synthetic fiber in the present invention using a reactive dye, a dyed product with extremely excellent color fastness can be obtained. The reactive dye of the present invention may be any ordinary reactive dye having a color-forming conjugate system and a reactive group that reacts with a functional group such as a hydroxyl group, an amino group, or an amide group possessed by fibers. Among such reactive dyes, use of dichlorotriazine dyes or fluorine-containing pyrimidine dyes provides excellent color value and color fastness. This tendency is particularly strong when alkali treatment is applied after dyeing, and items dyed using dichlorotriazine-based or fluorine-containing pyrimidine-based reactive dyes should be treated with alkali at 60 to 80°C. There is almost no discoloration due to dye loss,
Dyeings with extremely high hue stability can be obtained. Furthermore, in the present invention, after dyeing, alkali treatment or quaternary ammonium salt treatment is included in the constitution of the invention.
This process replaces the acidic groups in the modified synthetic fibers with alkali metals such as sodium and potassium to impart hydrophilic properties such as hygroscopicity, and is completely meaningless even if performed before dyeing. That is, since dyeing with the reactive dye according to the present invention is carried out on the acidic side, even if alkaline treatment is performed before dyeing, the material will be treated with acid again in the subsequent dyeing, and hydrophilic properties such as hygroscopicity will disappear. In addition, the alkali treatment is performed using an alkaline substance such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, or ammonia water in an aqueous solution at room temperature or heat treatment. When heat-treating, 60%
Preferred conditions are treatment at ~80°C for 20-60 minutes. In addition, if quaternary ammonium salt treatment is performed instead of alkali treatment, it is possible to impart hydrophilic properties such as hygroscopicity, as well as antibacterial and antibacterial properties, similar to alkali-treated products.
It will also be possible to have properties such as anti-fungal properties. Even in this case, if conventionally well-known acid dyes or disperse dyes are used for dyeing, the dye fastness will be very poor and it will be impractical. By dyeing with a dye, it is possible to obtain sanitary products with extremely high fastness, which is one of the major features of the present invention. In this case, the treatment conditions are similar to those in the alkali treatment using a quaternary ammonium salt such as lauryldimethylbenzylammonium chloride, bromide, lauryltrimethylammonium chloride, and bromide as an aqueous solution. Note that if this treatment is performed after the alkali treatment, the quaternary ammonium substitution efficiency will be further increased. In addition, in both alkali treatment and quaternary ammonium salt treatment, the above-mentioned compound has a
It is preferable to use the theoretical equivalent or four times the theoretical equivalent. In the present invention, synthetic fibers refer to synthetic fibers such as polyamide, polyacrylonitrile, and polyester. Polyamide refers to nylon 6, nylon 6/6, nylon 6/10, nylon 8, nylon 10, etc., polyacrylonitrile refers to ordinary acrylic, and polyester refers to terephthalic acid and ethylene glycol. Alternatively, it refers to ordinary polyesters made of butylene glycol, etc., or modified polyesters thereof. Furthermore, the acidic group in the present invention means a carboxyl group or a sulfone group. In the present invention, the method for introducing acidic groups of 3.3×10 ^-6 gram equivalent/gram fiber or more is a method of graft polymerizing a vinyl monomer having acidic groups, or There are methods such as mixed spinning or copolymerization of compounds such as vinyl monomers, but for polyamides and polyesters, the former method of graft polymerization is easier to industrialize, and for polyacrylonitrile systems, the latter method of fiber production is easier to industrialize. As a method for graft polymerization, the fibers are activated in advance by radiation irradiation or an aqueous solution or aqueous dispersion of a peroxide such as ammonium persulfate, potassium persulfate, or benzoyl peroxide, and then an acidic vinyl monomer aqueous solution is used. There is a method in which a radical initiator (peroxide) and a vinyl monomer having an acidic group coexist in the same bath as described above. Furthermore, if necessary, the reaction can be promoted even under relaxed conditions by adding a reducing substance such as hydrosulfite or a reaction product of sodium sulfoxylate and formalin to the reaction system. In addition, the vinyl monomer having an acidic group as used in the present invention includes vinyl carboxylic acid monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, butenetricarboxylic acid, allylsulfonic acid,
It refers to vinyl sulfonic acid compounds such as methallyl sulfonic acid and styrene sulfonic acid, and each may be used alone or in combination. Next, in the present invention, the amount of acidic groups introduced is 3.3×
Although it is limited to 10 ^-6 gram equivalent/gram fiber or more, if it is less than this, it is difficult to impart appropriate hygroscopicity and antistatic properties to the synthetic fiber. In the present invention, the forms of fibers include staple, tow, filament, spun yarn, knitted fabric, woven fabric,
It may be in any form, such as a web. As previously mentioned, reactive dyes have traditionally been used to dye cotton in the presence of alkali, such as vinyl sulfone, acrylamide, dichloroquinoxaline,
There are various types of dyes, such as dichlorpyridazone, monochlortriazine, dichlortriazine, trichlorpyrimidine, and monofluorodichlorpyrimidine, and all of them can dye cotton reliably. On the other hand, these reactive dyes can dye ordinary nylon in the presence of acid;
The dyeing speed is too fast and there is almost no migration of the dye, so it has extremely poor level dyeing properties, so it has not been applied at all, and it is reactive to ordinary polyacrylonitrile and polyester fibers. The reality is that dyes do not dye and are not used at all for normal dyeing. However, the modified polyamide synthetic fibers introduced with acidic groups according to the present invention have a unique feature in that the dyeing speed of the reactive dye is slowed down and the dyeing is much more level than that of ordinary nylon. Moreover, when dyed under acidic conditions and then treated with alkali, normal nylon shows a large decrease in dye fastness, whereas modified polyamide with acidic groups shows a large decrease in dye fastness. In addition to the effect of obtaining a highly durable and high-quality product with almost no dyeing, the hygroscopic property remains the same as that of an undyed product. In addition, as mentioned above, even in polyacrylonitrile fibers into which acidic groups have been introduced,
For modified polyacrylonitrile fibers containing dimethylaminoethyl acrylate, methacrylate, or acid dye-dyeable sheets such as diethylaminoethyl acrylate and methacrylate, the fastness The same can be said of modified polyester, which can be uniformly dyed and at the same time retain the hygroscopicity of the modified fiber. A specific example will be explained below. In addition, the color fastness in the examples was based on JIS L-0844. The moisture absorption rate was calculated from the weight change when a sample was completely dried at 110°C for 2 hours and left in an atmosphere of a saturated aqueous solution of sodium nitrite (20°C x 65% RH) for 1 day and night. Example 1, Comparative Examples 1 to 4 Woolly processed yarn made of nylon 6 with 70 denier and 24 filaments was knitted into a two-stage double-sided jersey.
This jersey was mixed with 30% owf of acrylic acid (wt% based on the weight of the material to be treated) and 1% owf of potassium persulfate.
Heating in a solution with a bath ratio of 1:30 and raising the temperature to 90℃.
The treatment was carried out for 60 minutes. The acrylic acid produced by this treatment undergoes graft polymerization, and the carboxyl group becomes 7.2×
10 ^-4 equivalents/gram fiber were introduced. Next, the modified nylon jersey was treated with a monofluorodichloropyrimidine-based reactive dye (C.I.
Reactive Red 86) 3% owf, acetic acid 1
It was immersed in a dye solution consisting of cc/ and dyed at 100°C for 60 minutes at a bath ratio of 1:30. Next, the dyed product is immersed in an aqueous solution consisting of 20% OWF sodium carbonate,
The treatment was carried out at 60° C. for 60 minutes by increasing the temperature. As shown in Table 1, this product became a jersey with good color fastness and high moisture absorption. As the next comparative example, the same jersey as in this example was graft-modified in the same manner as in this example, and then
Ordinary acid dyes (C.I. Acid Red)
114) It was immersed in a dye solution consisting of 3% owf and 1 c.c. of acetic acid and dyed at 100°C for 60 minutes at a bath ratio of 1:30. When the dyed product was then treated with alkali under the same conditions as in this example, the color fading was severe and the color fastness was low. Next, as Comparative Example 2, ordinary nylon jersey similar to this example was dyed under the same conditions as this example without graft modification, but the dyeing was too fast, resulting in uneven dyeing and reducing the commercial value. It became something that doesn't exist. Further, as Comparative Example 3, the moisture absorption rate was measured for the fiber of this example that was not dyed but only subjected to alkali treatment, and it showed the same moisture absorption rate as that of the fiber that was dyed and then treated with alkali. Next, as Comparative Example 4, nylon 6 jersey graft-modified in the same manner as in this example was
Eye Reactive Red 86 When dyeing with 3% owf, 7g/sodium hydroxide was added and dyeing was carried out in an alkaline bath at 100℃ for 60 minutes.
Almost no staining occurred.

[Table] Example 2 A polyacrylonitrile-based polymer obtained by copolymerizing acrylonitrile with 6 mol% of methyl acrylate, 8 mol% of acrylic acid, and 0.8 mol% of dimethyl liaminoethyl methacrylate was added to a dimethyl sulfoxide solvent in a conventional manner. Based on wet spinning,
The staples were 3 denier x 76 mm. The staple was made into a spun yarn of 48 count single yarn, and cheese dyeing was performed under the following conditions. In other words, C.I. Reactive Blue 3 (dichlorotriazine-based reactive dye) 3%
98℃ x 60 using a dye solution containing owf, acetic acid 1 c.c.
It was dyed using a package-type cheese dyeing machine for 1 minute (bath ratio 1:15). Next, the yarn was treated in an aqueous solution containing 10% OWF of dimethyl benzyl ammonium chloride at 80°C for 30 minutes to obtain a hygroscopic acrylic yarn with little discoloration and good color fastness. Moisture absorption rate 10.3% Washing fastness (color fading) Grade 4 Wet friction fastness Grade 4 Transfer fastness Grade 4 For comparison, C.I. Acid Blue 54 was used instead of the reactive dye in this example. The rest of the dyeing process was carried out under the same conditions as in this example, but the dyeing fastness was extremely poor.

Claims (1)

[Claims] 1. A synthetic fiber into which an acidic group or a salt thereof has been introduced in an amount of 3.3×10 ^-6 gram equivalent/gram fiber or more is dyed with a reactive dye in the presence of an acid. A method for dyeing modified synthetic fibers. 2. The method for dyeing modified synthetic fibers according to claim 1, wherein the reactive dye is selected from dichlorotriazine dyes and fluorine-containing pyrimidine dyes. 3. Claim 1 in which the dyeing treatment includes an alkali treatment step after the dyeing step with a reactive dye.
A method for dyeing modified synthetic fibers as described in Section 1. 4. The method for dyeing modified synthetic fibers according to claim 3, wherein the alkali treatment is treatment with a quaternary ammonium salt.