JPS6146592B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a dyeing method for obtaining a raised sheet material with extremely excellent fastness. In recent years, raised sheet products have been developed that are made of fiber-entangled nonwoven fabrics or raised knitted woven fabrics and elastic polymers contained therein, and at least one side of which is made up of napped fabrics mainly made of microfine fibers or napped fabrics made of microfine fibers and resin. is manufactured as a substitute for natural suede leather. In order to enhance the functionality of these napped sheets as fashion materials, it is required to diversify colors and improve their fastness. However, when fibers mainly consisting of ultrafine fibers are used as the constituent material of a raised sheet, the surface area of the fibers is extremely large, and one of the other constituent materials, such as polyurethane elastomer, acrylic ester resin, and other rubbers, The elastic body resin is 2
The secondary transition point is low, and when these resins are porous, the surface area is extremely large. In addition, the desorption rate is very fast, and if the dye has a certain distribution between the dyed object and the water or the dyed object and the solvent, the dye may not be absorbed into the washing liquid or dry cleaning liquid. There are disadvantages such as the desorption of the dye, which increases the color change of the dyed product, or the tendency of the desorbed dye to contaminate other items, which lowers the commercial value. Conventionally, there is a method to reduce the desorption of dyes into washing liquids and dry cleaning liquids by increasing the denier of ultrafine fibers so that a small amount of dye is sufficient for color development and slowing down the desorption speed. If it is made thicker, it has the disadvantage that it does not have the texture, touch, suppleness, napping, and luster similar to natural leather. There is also a method of coloring microfibers by adding substances that are insoluble or poorly soluble in water and solvents, such as carbon black coloring pigments, before spinning or impregnating resins. Although the adhesion to the dry cleaning solution is extremely small and the effect is sufficient, it is difficult to match the color of the fiber and the impregnated polymer, resulting in only an irritating result. It has drawbacks such as being difficult to make. Also,
A method has also been proposed in which the final product is dyed with a disperse dye, and then only the dye sorbed to the elastic polymer is treated in the presence of a chemical reducing agent to desorb it (see Japanese Patent Publication No. 38761/1983). ). however,
When using disperse dyes as in this method, the color of the elastomer is removed by the chemical reduction treatment agent, and the colors of the fibers and the elastomer are significantly different.
It causes irritation and has the drawback that it is difficult to obtain products with deep colors. In addition, as a method for obtaining a raised sheet material with excellent robustness,
One of the present inventors and other inventors has discovered a method of dyeing and brushing a raised sheet material with sulfur dye, vat dye, or sulfur vat dye, and a patent application has already been filed for this method. (Refer to Japanese Patent Application Laid-Open No. 1365-1983). According to this method, a napped sheet product with considerably excellent fastness can be obtained, but it is still not sufficient, and there has been a need for a dyeing method for obtaining a napped sheet product with even better fastness. The present invention is a method that satisfies the above-mentioned requirements, and more specifically, the present invention provides a method for applying a coloring substance having characteristics similar to color pigments that are hardly soluble in washing liquids and dry cleaning solvents through an industrially advantageous dyeing process. To obtain a raised sheet material having extremely excellent fastness. That is, the present invention provides a method for dyeing a napped sheet material which is mainly composed of a fiber aggregate and an elastic polymer contained therein, and which has napped fibers made of ultrafine fibers of 0.5 denier or less on at least one side thereof. () First, the raised sheet material is dyed with an alkaline aqueous solution of a dye that is reduced in the presence of an alkali and becomes water-soluble, () Then, after an oxidation treatment is performed to make the dye water-insoluble, () To obtain a raised sheet material having excellent color fastness by desorbing undyed dyes adhering to the raised sheet material by using a combination of chemical treatment and brushing treatment. According to the method of the present invention, dyes that are hardly soluble in water and dry cleaning solvents are reduced in the presence of an alkali and used as water-soluble forms, and the objects to be dyed are dyed in this state, which is relatively easy industrially. be. In addition, after dyeing, the dye is oxidized and returned to its original state, which is almost insoluble in water and dry cleaning solvents, so there is very little dye desorption into washing and dry cleaning solutions, and there is little discoloration or fading of dyed products. , and less likely to contaminate other things. However, the presence of undyed dyes or unoxidized dyes will reduce the abrasion fastness of dyed products. By combining treatment with brushing in the absence of hair, and by applying treatment in combination with soaping,
By desorbing only the undyed dye without desorbing any of the dyed dyes, it is possible to obtain a raised sheet material that has excellent fastness against washing, dry cleaning, perspiration, sublimation, friction, etc. . In particular, in the method of the present invention, the chemical desorption treatment of (1) above and
(2) By using brushing treatment, that is, a special treatment included in physical treatment, a significantly superior effect that cannot be obtained by using these treatments alone can be obtained. The method of the present invention is applicable to cases where the fibers constituting the napped sheet are ultrafine fibers of 0.5 denier or less, particularly 0.2 denier or less, especially 0.08 denier or less, or the dyeing behavior of the elastomeric polymer and the fibers is different. extremely effective in some cases,
The object of the present invention is achieved without causing disadvantages such as hardening of the hand, deterioration of the touch feeling, and deterioration of the writing effect. The raised sheet material used in the present invention includes entangled nonwoven fabric,
An elastic polymer is contained in a porous or non-porous state in a fiber aggregate such as a woven fabric, a knitted fabric, a raised fabric of these fabrics, or a fabric that is a combination of these, and at least one side of the fiber aggregate contains an elastic polymer of 0.5 denier or less. It is a sheet material with raised naps made of ultra-fine fibers. The fibers constituting the fiber polymer include polyamides such as 6-nylon, 66-nylon, 610-nylon, and aromatic polyamides, polyesters such as polyethylene tephthalate or its copolymers, polyolefins, and acrylonitrile-based fibers. It is made of one or more polymers selected from polymers, polyvinyl alcohol, cellulose, cellulose derivatives, etc. Examples of the elastic polymer include polyurethane or polyurethaneurea polymerized from a polymer diol, an organic diisocyanate, and a chain extender, a polyacrylic acid ester or a copolymer thereof, an acrylonitrile-butadiene copolymer, and a polymer diol and a carboxylic acid. Examples include polyester polymerized with a chain extender and other synthetic rubbers. The fluff on the surface may be made of ultrafine fibers of 0.5 denier or less, or may be made of such ultrafine fibers and other polymers.In short, ultrafine fibers are one of the constituent materials of the nap. It is acceptable as long as it fulfills the following criteria. In the method of the present invention, the dye used to dye the raised sheet material is reduced in the presence of an alkali,
These are water-soluble and include sulfur dyes, vat dyes, and sulfur vat dyes. As the alkali, for example, caustic soda, soda carbonate, etc. are used, and as the reducing agent, for example, hydrosulfite, Rongarit C (sodium sulfoxylate formaldehyde), Rongarit CL, sodium hydrogen sulfide, sodium sulfide, etc. are used alone or in combination. You can. The dye, which has been reduced in the presence of an alkali and has become water-soluble, is prepared in accordance with the desired color and concentration and used as a dye liquor. Dyeing is usually carried out at a dye liquor temperature of 40 to 100°C, preferably 60 to 95°C, but the dye liquor may be kept at the above temperature in advance, or the dyeing liquor may be kept at the above temperature after immersing the dyed object. The temperature may be increased within the temperature range. The immersion time is 3 seconds or more, preferably about 5 seconds to 120 minutes. If necessary, dyeing may be carried out by adding a dye solution. Then, after squeezing or draining the dye solution, air oxidation or chemical oxidation is performed. If necessary, air oxidation or chemical oxidation may be performed after the dye liquor has been squeezed or drained, washed with water or neutralized with an alkali. As the oxidizing agent, those commonly used in dyeing factories, such as potassium dichromate, potassium permanganate, and perboric acid, can be used in the method of the present invention. Next, the dyed material is soaped if necessary, and then undyed dye is removed by chemical treatment and brushing treatment. Chemical desorption treatment involves immersing the dyed product in an aqueous solution of a chemical reducing agent, such as hydrosulfite soda, Rongarit C, Rongarit CL, dechlorin, hydrosulfite calcium, acidic sodium sulfite, etc. This is a method of including such an aqueous solution. Also, what is brushing processing?
A method of brushing a dyed product immersed in water or with water or without water using a bristle brush with or without abrasive grains, preferably with water. This is a method of brushing in the presence of. In the method of the present invention, either the chemical desorption treatment or the brushing treatment may be performed first. By using these two dyeing methods together, the undyed dye is chemically and physically removed, and the fastness is significantly improved. The dyed products obtained in this way have markedly improved fastness to rubbing, fastness to washing, fastness to dry cleaning, and fastness to perspiration compared to those dyed with conventional metal complex dyes and acid dyes alone. In order to finely adjust the hue and reduce irritability, it may be dyed with at least one dye selected from metal complex dyes, acid dyes, disperse dyes, direct dyes, and reactive dyes. By dyeing twice in this way, the amount of at least one dye selected from metal complex dyes, acid dyes, disperse dyes, reactive dyes and direct dyes can be reduced when dyeing with these dyes only once. As a result, the amount of dyeing on the napped sheet material is also significantly reduced, so the amount of dyeing that comes off during washing and dry cleaning is also significantly reduced, and the fastness is significantly lower than that of dyed products alone. improves. In addition, by dyeing twice, the color irritation of the napped sheet material is further improved, and a napped sheet material with a deeper color can be obtained. Further double dyeing results in a raised sheet material that is much more flexible than without double dyeing. The present invention will be explained below with reference to examples, but the present invention is not limited to these examples. In the examples, parts and % are values based on weight. Example 1 The napped surfaces of the ultrafine fibers were formed on both surfaces of a base body containing a polyurethane elastomer in an entangled nonwoven fabric of nylon fibers of an ultrafine fiber bundle in which about 750 ultrafine fibers with an average fineness of about 0.003 denier were bundled. When dyeing the formed raised sheet material having a thickness of 0.70 mm, the following treatment was performed. () Dyeing process Dye bath composition Dye Mikethrene Brilliant Violet RR (Mitsui Toatsu) 0.5% soln. Alkali Caustic soda (30°B'e) 3% Reducing agent Hydrosulfite soda
2% Penetrant Elecanthol AS (Bayer) 0.2% Dyeing conditions Dyeing temperature 80°C Dyeing time 10 seconds Squeezing rate 70% The raised sheet treated under the above conditions was then air oxidized, washed with water, and further oxidized with a chemical solution. () Chemical oxidation process Bath composition Hydrogen peroxide solution (35%) 0.2% soln. Acetic acid (48%) 0.2% (14) Treatment conditions Bath temperature 60℃ Treatment time 10 minutes After treatment, remove treatment agent etc. by washing with water , the unstained stain was removed by the following treatment. (-1) Chemical desorption treatment process Treatment bath composition Hydrosulfite soda 0.3% soln. Sodium carbonate 0.5% Amirazine (Daiichi Kogyo Seiyaku) 0.1% Treatment conditions Bath temperature 60℃ Treatment time 15 minutes Treated raised sheet After washing the object with water to remove the processing agent, etc., the next brushing treatment was performed. (-2) Brushing treatment Brushing is done underwater with a nylon bristle brush roll, and the dye attached to the surface is removed.
Remove unattached dye, fallen fluff, etc. Various fastnesses of the raised sheet material (product of the present invention) obtained through the above steps were measured. The results are shown in Table 1. At the same time, in the above process, (-
Napped sheet products obtained by omitting only the desorption treatment steps of 1) and (-2) (comparative example product A), (-1)
Various types of raised sheet products obtained by omitting only the chemical desorption treatment step (Comparative Example Product B) and raised sheet products obtained by omitting only the brushing treatment step (-2) (Comparative Example Product C) The fastness is also listed in Table 1.

[Table] Example 2 When dyeing the raised sheet material of Example 1, the following treatment was performed. () Dyeing process Dye bath composition Dye Hydrosol Green 3B (I.
CI) 3% soln. Reducing agent Sodium hydrogen sulfide 1.5% Penetrating agent Elecanthol AS (Bayer) 0.2% Dyeing conditions Dyeing temperature 80℃ Dyeing time 5 seconds Squeezing rate 70% The raised sheet treated under the above conditions was then After air oxidation and washing with water, the following chemical oxidation was performed. () Chemical oxidation process Bath composition Hydrogen peroxide solution (35%) 0.2% soln. Acetic acid (48%) 0.2% Treatment conditions Bath temperature 60℃ Treatment time 10 minutes The treated raised sheet was washed with water and treated with treatment agent. After removing such substances, the following brushing treatment was performed. (-1) Brushing treatment Brushing in water with a nylon bristle brush roll removes the dye attached to the surface.
Remove unattached dye, fallen fluff, etc. The brushed raised sheet was subjected to the following treatment to completely remove the undyed dye. (-2) Chemical desorption treatment process Treatment bath composition Hydrosulfite soda 0.1% soln. Sodium carbonate 0.5% Amirazine (Daiichi Kogyo Seiyaku) 0.1% Treatment conditions Bath temperature 50°C Treatment time 10 minutes After treatment, washing with water removes the treatment agent. After removing the material, the width of the sheet material was determined, the material was dried, and a post-finishing treatment was performed to obtain a dyed napped sheet material. Various fastnesses of the thus obtained raised sheet material (product of the present invention) were measured.
The results are shown in Table 2. At the same time, in the above steps, a raised sheet product obtained by omitting only the desorption treatment steps (-1) and (-2) (comparative example product D), omitting only the chemical desorption treatment step (-2) Raised sheet material (comparative example product E) and (-
Table 2 also shows various fastnesses of the raised sheet product (comparative example product F) in which only the brushing treatment step in 1) was omitted.

[Table] Example 3 The four types of napped sheet products dyed in Example 2, ie, the product of the present invention, Comparative Example Product D, Comparative Example Product E, and Comparative Example Product F, were further subjected to the following dyeing. () Dyeing process Metal complex dye lanasin green as dye
Using 5GL1.5%owf, dye bath ratio 1:50, temperature 90
℃, time 60 minutes, dyed green, then detergent monogen 1g/bath ratio 1:50, temperature 60℃
After soaping for 20 minutes, it was washed with water, the width was determined and dried, and a post-finishing treatment was performed to obtain a raised sheet. Various fastnesses were measured for each of the obtained raised sheet products. The results are shown in Table 3 below.

[Table] The product of the present invention had a deep green color, and was a napped sheet product with excellent fastness and excellent texture and texture.

Claims (1)

[Scope of Claims] 1. Dyeing a raised sheet material that is mainly composed of a fiber aggregate and an elastic polymer contained therein, and that has raised naps made of ultrafine fibers of 0.5 denier or less on at least one side thereof. () First, the raised sheet material is dyed with an alkaline aqueous solution of a dye that becomes water-soluble by being reduced in the presence of an alkali, () Then, after oxidation treatment is performed to make the dye water-insoluble, ( ) Chemically treating the undyed dye adhering to the raised sheet material with at least one reducing agent selected from hydrosulfite soda, Longalitz C, Longalitz CL, dechlorin, hydrosulfite calcium, and acidic sodium sulfite. A method for dyeing a napped sheet material, characterized in that it is desorbed by a combination of brushing treatment and brushing treatment. 2. The dyeing method according to claim 1, wherein the elastic polymer is a polyurethane elastomer. 3. The dyeing method according to claim 1 or 2, wherein the dye is at least one selected from sulfur dyes, vat dyes, and sulfur vat dyes. 4. When dyeing a napped sheet material that is mainly composed of a fiber aggregate and an elastic polymer contained therein, and which has napped fibers made of ultrafine fibers of 0.5 denier or less on at least one side, () The raised sheet material is dyed with an alkaline aqueous solution of a dye that becomes water-soluble by being reduced in the presence of an alkali, () The raised sheet material is then subjected to an oxidation treatment to make the dye water-insoluble, and () the raised sheet material is dyed. The adhering undyed dye is chemically treated with at least one reducing agent selected from hydrosulfite soda, Longalitz C, Longalitz CL, dechlorin, hydrosulfite calcium, and acidic sodium sulfite in combination with brushing treatment. () Further, the raised sheet is dyed with at least one dye selected from metal complex dyes, acid dyes, disperse dyes, reactive dyes, and direct dyes. dyeing method. 5. The dyeing method according to claim 4, wherein the elastic polymer is a polyurethane elastomer. 6. According to claim 4 or 5, the dye that becomes water-soluble when reduced in the presence of an alkali is at least one selected from sulfur dyes, vat dyes, and sulfur vat dyes. Staining method described.