JP4328287B2 - Textile processing method - Google Patents

Description

  In the present invention, a mixture of a permanganate and a particulate inorganic salt is brought into contact with a fiber product before or after dyeing to remove fluff or fibrils that significantly lower the quality of the fiber product, thereby improving the quality of the fiber product. Regarding the method.

Textile products are usually processed after dyeing or resin processing, and the amount of fluff or fibrils generated in this process is one of the important indicators for determining the quality of textile products. .
In particular, processing of easily fibrillated fibers such as polynosic fibers and solvent-spun cellulose fibers or fiber products obtained by blending and knitting these fibers requires a process for removing the generated fibrils. Usually, this process is mainly carried out by so-called bioprocessing which is removed using an enzyme agent such as cellulose. For example, an alkaline solution is applied to solvent-spun cellulose fiber or its structure to swell the fiber. A method is disclosed in which fibrils are expressed by mechanical force and then cellulase is applied to cut the fibrils (see Patent Document 1). However, this method requires a long time for processing and the fiber diameter. Even if the thin fibrils can be easily removed, if the surface of the fiber product is made clear by removing even the fluff with a large fiber diameter, there will be a significant drop in strength, which makes it difficult to adapt to thin fiber products. It is left behind and its usage and usage are limited.

  In recent years, from the viewpoint of diversification of consumer needs and fashionability, these fiber products are also found in spot dyeing and denim clothing that artificially generate spots different from uniform dyeing, printing or discharging. A method of scraping off the dye on the surface of the fiber with pumice, such as stone washing, or a textile product that has a wash-like appearance by treating it with a chlorine-based bleaching agent such as hypochlorite in a uniform fade tone, After exhaustive dyeing of pigments, it is also desired to develop a variety of textile products that have a special dyeing effect of wash-out using the property of the pigments being easily removed. However, the method of scraping the dye on the surface of the fiber with pumice stone, or the method of treating with a chlorinated decoloring agent such as hypochlorite in a uniform fade tone, does not damage the fiber. It is limited to large denim garments that are relatively thick. In addition, in the method using pigments, the stain of the dyeing machine during exhaust dyeing is large, and it is necessary to use a resin for fixing the final pigment, which makes the process complicated, even if a resin is used However, the fastness to washing or the fastness to friction was poor, and there was a drawback that it was limited to light colors and intermediate colors.

Easily fibrillated fibers such as polynosic fibers and solvent-spun cellulose fibers are particularly deteriorated due to the generation of fluff and fibrils, so there is little damage to the fibers along with removal of the generated fibrils, and uniform dyeing, There has been a demand for a processing method that can be applied to various colors such as printing, discharging and washing.
Japanese Patent Laid-Open No. 11-140772

  The object of the present invention is to effectively remove fluffs and fibrils generated in easily fibrillated fibers such as polynosic fibers and solvent-spun cellulose fibers without damaging the fibers, or fiber products obtained by blending and knitting these fibers, It is an object of the present invention to provide a processing method that can be applied to a variety of washing-like colors for textile products dyed simultaneously.

  As a result of intensive studies to solve the above problems, the present inventors have found that fluff or fibrils generated in a fiber product can be effectively removed by bringing the mixture of permanganate and granular inorganic salt into contact with the fiber product. In addition, the above-mentioned object of simultaneously performing various coloring processes was achieved by treating the textiles dyed with dyes having different decolorizing properties with respect to permanganate.

That is, the first method of the present invention is to bring a mixture of permanganate and granular inorganic salt, which is a diluent thereof, into a fiber product made of easily fibrillated fibers before dyeing, and in a desizing scouring bleaching step or the like. This is a processing method that effectively removes fluff or fibrils generated on the surface of the fiber product and obtains a high-quality fiber product that does not generate fuzz or fibrils in the subsequent steps.
The second method is a mixture of permanganate and granular inorganic salt, which is a diluent thereof, to a fiber product comprising easily fibrillated fibers dyed in advance with dyes having different decolorizing properties with respect to permanganate. Is a textile processing method for removing fluff or generated fibrils on the surface of the textile product and decolorizing the textile product.

  According to the dyeing and processing method of the present invention, fluff and fibrils generated in easily fibrillated fibers such as polynosic fibers and solvent-spun cellulose fibers, or fiber products obtained by blending and knitting these fibers are effective without damaging the fibers. For products that can be removed at the same time and dyed at the same time, it is possible to express a wide range of colors from light to heavy, such as uniform dyeing, printing, discharging and washing.

The fiber product referred to in the present invention is an easily fibrillated fiber such as polynosic fiber or solvent-spun cellulose fiber, or vegetable fiber such as cotton or hemp, animal fiber such as wool or silk, viscose rayon, A woven fabric or knit blended with synthetic fiber such as recycled cellulose fiber such as copper ammonia rayon, polyester fiber, polyamide fiber or acrylic fiber, and a sewn product obtained by sewing them can be used.
As the permanganate used in the present invention, an alkali metal salt or an alkaline earth metal salt can be preferably used. Specific examples include lithium permanganate, potassium permanganate, sodium permanganate, magnesium permanganate, calcium permanganate and the like, with potassium permanganate being common. These permanganates are usually obtained as crystal lumps, but in the present invention, they are preferably granulated and used from the viewpoint of the effect.

  The granular inorganic salt plays an important role in bringing the permanganate as a diluent for the permanganate in an appropriate and uniform contact with the fiber product. Alkali metal or alkaline earth metal hydrochlorides and sulfates Nitrate can be used. Specific examples include lithium chloride, potassium chloride, sodium chloride, magnesium chloride, calcium chloride, lithium sulfate, potassium sulfate, sodium sulfate, magnesium sulfate, calcium sulfate, lithium nitrate, potassium nitrate, sodium nitrate, magnesium nitrate, and calcium nitrate. However, sodium sulfate is commonly used as a dyeing aid for reactive dyes.

  In the present invention, these permanganate particulates and granular inorganic salts are added to the fiber product for treatment. However, when the permanganate is brought into contact with the fiber product in a high purity state, the fiber product has a remarkable strength. It is not preferable because it causes a decrease, and it is preferably used as a diluted permanganate granular material diluted with an inorganic salt. In addition, since the sufficient amount of permanganate added to the dry weight of the textile product is 0.01 to 1.0% by weight and a sufficient effect can be obtained, a product diluted with granular inorganic salt to about 10% by weight in advance is used. It is preferable to use it because there are few measurement errors and mixing with the particulate inorganic salt is easy. As such a diluted permanganate granular material, GS-KP (trade name, Sun Chemical Co., Ltd.) in which potassium permanganate was diluted with sodium sulfate and the content of potassium permanganate was 10% by weight. Made). GS-KP can be suitably used as the permanganate granular material of the present invention. In order to dilute the permanganate, a granular inorganic salt can be further added to the granular mixture of the permanganate and the inorganic salt. Further, the dry weight of the fiber product in the present invention is the weight of the fiber product in a standard state (temperature 20 ° C., relative humidity 65%).

  Next, a specific processing method will be described. In the case of the first method, the object to be treated is a fiber product that has been subjected to pre-dyeing treatment such as uniform scouring, scouring and bleaching before uniform dyeing, printing, dyeing or spotting. The contact treatment of the mixture of the permanganate and the particulate inorganic salt and the textile product is performed in a dynamic state in order to obtain an appropriate homogeneity, but the stop for several seconds to several minutes may be repeated. The apparatus is not particularly limited as long as a dynamic state can be obtained, but a tumbler, a washer, or the like can be preferably used. The fiber product that has been pre-dyed is put into these rotating devices and contact-treated in a wet state. The wet fiber product in the present invention is a fiber product having a drawing ratio of 30% to 150%, preferably It is a textile product with a drawing rate of 50% to 100%. The granular inorganic salt is previously prepared in a weight of 1 to 5 times the dry weight of the fiber product, and the amount of permanganate used is 0.01 to 1.0% by weight based on the dry fiber product. GS-KP (manufactured by Sun Chemical Co., Ltd.) in an amount of 0.1 wt% to 10 wt%, preferably 0.3 wt% to 7 wt%, together with the granular inorganic salt, is put into a rotating device and stirred well. The wet textile product is put into this, and the operation is performed at room temperature for 5 to 60 minutes, preferably 10 to 40 minutes.

  The contact-treated fiber product has water-insoluble manganese dioxide, which is the reaction product of permanganate and organic substances such as fibers, so it is washed to remove unreacted permanganate and inorganic salt. After removal, a fiber product from which fluff or fibrils have been removed can be obtained by removing it by a known method, i.e., treatment with a reducing agent. After removing manganese dioxide by treating with a reducing agent, etc., if these are uniformly dyed, printed, discharged or spotted by known methods, these high-quality fiber products with minimal fuzz and fibrils can be obtained. I can do it.

  The reaction mechanism by which fluff or fibrils are removed is not clear, but is probably related to the concentration distribution of permanganate, a strong oxidant. Since the reaction proceeds in a semi-dry state in the present invention, permanganate dissolved in a small amount of water progresses to dry over time (it seems to be related to the dehydrating action of the granular inorganic salt) and moves to the fiber surface. To do. That is, it is considered that the permanganate concentration in the fluff and fibrils increases, and the polymer chain scission reaction and physical stagnation are synergistically removed.

  Furthermore, a second method for simultaneously removing fibrils and decolorizing textiles will be described. In this method, the object to be treated is a textile product that has been uniformly dyed, printed, discharged or spotted, and dyeing is carried out from a dye species that exhibits easy to difficult decoloration to permanganate. Can be selected and performed in a known manner. Examples of these dyes include direct dyes, sulfur dyes, acid dyes, and reactive dyes. Reactive dyes that have various hues and are widely used mainly for dyeing cellulose fibers are preferably used. I can do it.

  As an example, reactive dyes include reactive dyes that are easily decolorizable to permanganate, such as Sumifix Brillant Orange 3R (manufactured by Sumitomo Chemical Co., Ltd.). , Sumifix Red B (Sumifix Red B, manufactured by Sumitomo Chemical Co., Ltd.), Sumifix Brilliant Red BB (Sumifix Brillant Red BB, manufactured by Sumitomo Chemical Co., Ltd.), Cibacron Red FN-2BL (Cibacron Red FN-2BL) , Ciba Specialty Chemicals Co., Ltd.), Sumifix Brilliant Blue R (Sumifix Brillannt Blue R, Sumitomo Chemical Co., Ltd.), Sumifix Supra Blue BRF (Sumitomo Chemical Co., Ltd.) ), Cibacron Brillant Blue FN-G (Cibacron Brillant Blue FN-G, Ciba Specialty) Ti Chemicals Co., Ltd.), Cibacron Blue FN-R (Cibacron Blue FN-R, Ciba Specialty Chemicals Co., Ltd.), Reanova Blue CA (ReaNova Blue CA, Dystar Japan Co., Ltd.), etc. Can be mentioned.

  Examples of reactive dyes that exhibit difficulty in decolorization include Sumifix Yellow GR (Sumifix Yellow GR, manufactured by Sumitomo Chemical Co., Ltd.), Sumifix Supra Yellow 3RF (Sumifix Supra Yellow 3RF, manufactured by Sumitomo Chemical Co., Ltd.) , Cibacron Yellow FN-2R (Cibacron Yellow FN-2R, manufactured by Ciba Specialty Chemicals Co., Ltd.), Reanova Yellow CA (ReaNova Yellow CA, manufactured by Dystar Japan Co., Ltd.), Sumifix Supra Red 3BF (Sumifix Supra Red 3BF, manufactured by Sumitomo Chemical Co., Ltd.), Cibacron Red FN-R (Cibacron Red FN-R, manufactured by Ciba Specialty Chemicals), ReaNova Red CA (manufactured by ReaNova Red CA, manufactured by Dystar Japan) Sumifix Supra Blue E-XF (manufactured by Sumitomo Chemical Co., Ltd.) , Mention may be made of the Reanova Neivui CA (ReaNova Navy CA, manufactured by DyStar Japan Co., Ltd.), and the like.

  Next, decolorization and removal of fluff or fibrils are performed, but these reactions proceed simultaneously, and if performed in the same manner as in the first method described above, fluff and fibrils can be minimized and the quality can be reduced by appropriate decolorization. It is possible to obtain a fiber product having a high natural wash-out appearance. After removing manganese dioxide by treatment with a reducing agent, etc., it moves to steps such as soaping, resin processing, finishing oil treatment, etc., as necessary, but these steps are not particularly limited and are general methods Can be done.

  In the present invention, a mixture of permanganate and a granular inorganic salt that is a diluent thereof is brought into contact with a wet textile product in a dynamic state, and fluff or fibrils generated on the surface of the textile product in the process up to dyeing are removed. If a dye is appropriately selected, fluff or fibrils can be removed, and a textile product having a washed-out appearance that is spotted and having high quality can be obtained. Further, since the reaction proceeds in a semi-dry state in this processing method, damaged fibers remain only in a very shallow portion of the fiber product surface, and the influence on the product strength can be minimized.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to this range. In addition, the measurement of the quality and dough strength in this example was based on the following method.
・ Quality The sample was visually judged by five inspectors, and was judged in accordance with the following criteria.
◯: Less appearance of fluff and fibrils and excellent appearance.
(Triangle | delta): Although generation | occurrence | production of a fibril is few, a fluff is somewhat conspicuous and an external appearance is a little inferior.
X: Generation | occurrence | production of fluff and a fibril is large and an external appearance is inferior.
・ Fabric strength JIS L 1018 8.17A method (Mulen method)

[Example 1]
Tencel (registered trademark) No. 80 double yarn tenji knit fabric samples were prepared and used as Sample 1, Comparative Sample 1, and Comparative Sample 2, respectively. Using a Shinzen-type washing machine (model: mini testing machine) manufactured by Jinmae Iron Works Co., Ltd. as a device, 1 g / liter of brand name Espitol BSconc (manufactured by Sun Chemical Co., Ltd.) as a scouring agent and 2 g of sodium carbonate After scouring at a bath ratio of 1:20 and 80 ° C. for 30 minutes in a treatment bath containing 1 liter / liter, the sample 1 was dehydrated to a squeeze rate of 80% and then 2.5 times the dry weight of the sample 1 in advance. Thoroughly stir by adding to the Shinzen-style washing machine (model: mini-tester) manufactured by Jinzen Iron Works Co., Ltd., with a weight of granular sodium sulfate and 2.5% by weight of GS-KP based on the granular sodium sulfate. Then, the dehydrated sample 1 was added thereto, and contact treatment was performed at room temperature for 30 minutes. After the contact-treated sample 1 was taken out and washed with water, the bath ratio was 1:20 at 60 ° C. in a treatment bath containing the product name GS-N (manufactured by Sun Chemical Co., Ltd.) which is a reducing agent of 2.5 g / L. After treating for 15 minutes, it was washed with water to remove manganese dioxide adhering to the sample 1 by water solubilization and washing with water.

  Separately, using the same apparatus as the scouring treatment for Comparative Sample 1, 1.5 g / liter of Cellulizer-HP (manufactured by Nagase Seikagaku Co., Ltd.), which is an enzyme agent containing cellulase, and 0.1% acetic acid. In a treatment bath containing 5 g / liter and 1.0 g / liter sodium acetate at a pH of 5.2, the bath ratio is 1:20, treated at 50 ° C. for 60 minutes, washed with water, and then at 90 ° C. for 10 minutes. And washed with water. Next, scouring treatment, contact treatment, reduction treatment sample 1 was added with scouring treatment, enzyme treatment, deactivation treatment comparative sample 1 and scouring treatment comparison sample 2, and Sumifix Supra Yellow 3RF (150%, Sumitomo Chemical Co., Ltd.) was 0.86% by weight based on the total of sample 1, comparative sample 1 and comparative sample 2, Sumifix Supra Brillant Red 3BF 150%, Sumitomo Chemical ( Co., Ltd.) is 0.73% by weight with respect to the sum of sample 1, comparative sample 1 and comparative sample 2, and Sumifix Supra Blue 3BRF (Sumifix Supra Blue BRF 150%, manufactured by Sumitomo Chemical Co., Ltd.) 1, 0.62% by weight of the dye based on the total of Comparative Sample 1 and Comparative Sample 2 was mixed and dyed in accordance with the dyeing method of the reactive dye, and further a 2 g / L soaping agent. A product that is 2 g / L of finished oil, soaped and washed in a treatment bath containing Tripon P-60 (manufactured by Yushi Co., Ltd.) at a bath ratio of 1:20, 80 ° C. for 15 minutes. Sample 1, Comparative Sample 1 and Comparative Sample 2 which were oil-treated in a treatment bath containing the name FS-W-100 at a bath ratio of 1:20 at 50 ° C. for 10 minutes, and then dehydrated and dried and uniformly dyed dark brown Got. Table 1 shows the measurement results of the quality of the sample 1, the comparative sample 1, and the comparative sample 2, and the dough strength.

  As is apparent from Table 1, the sample 1 of the present invention was a high-quality sample in which fluff and fibrils on the sample surface were minimized and uniformly dyed dark brown. The comparative sample 1 which does not depend on, although fibril generation is suppressed, is slightly fuzzy, slightly inferior in fabric strength, and if the enzyme concentration is increased for the purpose of removing more fluff, the fabric strength becomes less than the practical strength. It was a sample of slightly inferior quality that was dyed dark brown. Comparative sample 2 was an inferior sample in which fluff and fibrils were generated on the entire surface of the sample and dyed dark brown. Further, as can be seen from Table 1, the dough strength of the sample 1 of the present invention is slightly decreased as compared with the comparative sample 2 without contact treatment and enzyme treatment, but such a decrease is a problem in practice. It is not a thing.

[Example 2]
Two 80-twisted yarn knitted fabric samples of 70% Tencel (registered trademark) and 30% cotton were prepared. One was sample 2 and the other was comparative sample 3. After scouring and bleaching by an ordinary method, Sample 2 was subjected to contact treatment and reduction treatment in the same manner as in Example 1. Next, sample 2 and comparative sample 3 were obtained by adding comparative sample 3 to sample 2 and dyeing, soaping, oil treatment, and drying in the same manner as in Example 1 and uniformly dyed dark brown. Table 2 shows the results of measurement of the quality and dough strength of the obtained sample 2 and comparative sample 3.

  As is apparent from Table 2, Sample 2 of the present invention is a high-quality sample that is evenly dyed dark brown with minimal fluff and fibrils on the sample surface even if it is a blended sample of Tencel and cotton. On the other hand, Comparative Sample 3 not according to the present invention was a sample of inferior quality in which fluff and fibrils were generated on the entire surface of the sample and dyed dark brown. Further, as can be seen from Table 2, the fabric strength is slightly decreased in Sample 2, but this decrease is not a practical problem.

Example 3
Two 60-twisted yarn woven knit fabric samples of 70% Tencel (registered trademark) and 30% wool that had been shrink-proofed were prepared, one of which was used as sample 3 and the other was used as comparative sample 4. After scouring and bleaching by the usual method of processing a sample mixed with wool, Sample 3 was subjected to contact treatment and reduction treatment in the same manner as in Example 1. Subsequently, the comparative sample 4 was added to the sample 3, and ReaNova Yellow CA (ReaNova Yellow CA, manufactured by Dystar Japan Co., Ltd.) was 0.78% by weight with respect to the total of the sample 3 and the comparative sample 4, and ReaNova Red CA (ReaNova Red CA, manufactured by Dystar Japan Co., Ltd.), sample 3 and comparative sample 4, 0.74% by weight and ReaNova Blue CA (ReaNova Blue CA, manufactured by Dystar Japan Co., Ltd.), sample 3, compared Sample 3 and comparative sample dyed uniformly in dark brown by dyeing, soaping, oil treatment and drying in the same manner as in Example 1 except that 0.51% by weight of the dye was added to the total of Sample 4 4 was obtained. Table 3 shows the measurement results of the quality of the sample 3 and the comparative sample 4 and the fabric strength.

  As is apparent from Table 3, the sample 3 of the present invention is a high-quality sample that is evenly dyed dark brown with minimal fluff and fibrils on the sample surface even if it is a blended sample of Tencel and wool. On the other hand, Comparative Sample 4 not according to the present invention was a sample of inferior quality in which fluff and fibrils were generated on the entire surface of the sample and dyed dark brown. Further, as can be seen from Table 3, the fabric strength is slightly decreased in the sample 3, but such a decrease is not a problem in practice.

Example 4
The sample of Example 1 was scoured in the same manner as in Example 1, and Sumifix Brilliant Red BB 150% (Sumifix Brillant Red BB, manufactured by Sumitomo Chemical Co., Ltd.) showing easy decolorization with respect to permanganate was used as a sample. Cibacron Yellow FN-2R (Cibacron Yellow FN-2R, manufactured by Ciba Specialty Chemicals Co., Ltd.), which is 2.4% by weight and hardly decolorizable to permanganate, is 0.9% of the sample. Two samples were prepared by blending wt% and dyeing in a conventional manner and soaping in the same manner as in Example 1. One was used as sample 4 and the other was used as comparative sample 5. Sample 4 was subjected to a contact treatment and a reduction treatment in the same manner as in Example 1, and then a treatment bath containing a trade name of Tripon P-60 (manufactured by Yushi Kogyo Co., Ltd.) as a 1 g / L soaping agent. The bath was soaked in water at a bath ratio of 1:20 at 80 ° C. for 15 minutes. Subsequently, the comparative sample 5 was added, oil-treated, and dried to obtain a dyed sample 4 and a comparative sample 5. Table 4 shows the measurement results of the quality of the sample 4 and the comparative sample 5 and the fabric strength.

  In sample 4, only the red dye that is easily decolorizable to permanganate has been decolorized, so the decolored area is yellow, and the contrast with the undecolored red is gorgeous, yet it has a natural wash-out tone. As is apparent from Table 4, the sample was high quality with less generation of fluff and fibrils. Comparative sample 5 was a sample of inferior quality in which fluff and fibrils were generated on the entire surface of the sample and were uniformly dyed yellow-red. Further, as can be seen from Table 4, the fabric strength of the sample 4 is slightly decreased, but such a decrease is not a problem in practice.

  According to the processing method of the present invention, fluffs and fibrils generated in easily fibrillated fibers such as polynosic fibers and solvent-spun cellulose fibers, or fiber products obtained by blending and knitting these fibers can be effectively prevented without damaging the fibers. At the same time, the fibrils can be removed from the dyed fiber product by such treatment, and various colors can be expressed such as discharging and washing.

Claims (2)

A method for processing a fiber product, comprising bringing a mixture of a permanganate and a particulate inorganic salt into contact with a fiber product made of easily fibrillated fibers to remove fluff on the surface of the fiber product or generated fibrils. A mixture of the permanganate and particulate inorganic salt, by contacting the fiber product made of easily fibrillated fibers dyed with dyes exhibiting different bleaching properties against permanganate, fluff or generation of textile surfaces A method for processing a textile product, wherein the fibril is removed and the textile product is decolorized.