JP5230894B2 - Composite material dyeing method and composite material dyed by the method - Google Patents

Description

  The present invention relates to a method for dyeing a composite material containing synthetic polyamide fiber, for example, a composite material containing synthetic polyamide fiber and cellulose fiber, polyacrylic or polyester, etc. The present invention relates to a method for dyeing the same color or a sharp different color, or a method for dyeing a clear white residue.

  In recent years, with the diversification of consumption trends for textile products, demand for composite materials has increased. Each fiber material that constitutes these composite materials often differs greatly in dyeing properties to dyes, so a method of dyeing each fiber material separately in a separate bath is adopted, but in this method , The process becomes long and economically disadvantageous. Therefore, there has been a demand for a dye and a dyeing method that can dye the composite material in the same color by a one-bath system.

  The present inventors have used a method of dyeing a composite material composed of synthetic polyamide fiber and cellulose fiber with a reactive dye that is covalently bonded to cellulose fiber in a thick and robust manner by using a large amount of sodium sulfate. No. 97777), and a neutral dyeing method and a dyeing method for dyeing of synthetic polyamide fibers in neutrality and acidity, and a reactive dye having a corrected color difference within a specific range (Japanese Patent Laid-Open No. 2002-194680) By using these methods, the composite material can be dyed in the same color by a one-bath system.

  However, for composite materials, in addition to dyeing with the same color, it is extremely added by different color dyeing that dyes each material in a clear different color, and white leaving dyeing that leaves one component fiber in the composite material undyed. Expected to yield valuable dyed products. Therefore, in addition to the above-described method of dyeing the same color, development of a different color dyeing method and a white-remaining dyeing method is desired.

In addition, for uniforms of military uniforms and rangers that have been used mainly for cellulose fibers, it has been desired to apply composite materials such as synthetic polyamide / cellulose that are oriented toward functionality, weight reduction, and durability. Development of a method for dyeing composite materials into so-called camouflage colors is also desired.
JP-A-7-97777 JP 2002-194680 A

  The present invention relates to a method of dyeing a composite material containing synthetic polyamide fibers in the same color or a sharp different color by hybrid dyeing in a one-bath system of different dyes, or a clear white residue dyeing on the composite material. It is an object to provide a method for performing (Problem 1). Another object of the present invention is to provide a composite material with high added value dyed by the dyeing method (Problem 2).

Problem 1 above is
6-Nylon jersey and un mercerized cotton knit in a 1: 1 weight ratio,
In a dyeing bath having a pH of 6.3 to 7.0 and a bath ratio of 1:20 to which 40 to 80 g / l of sodium sulfate is added, 5% o. w. f. , 10% o. w. f. For dyes other than Navy and Black dyes, 2% o. w. f. The density of 6-nylon jersey when dyed with NPA is NPA, and the density of unsilqueted cotton knit is NC,
Sodium sulfate 40-80 g / l and acetic acid 1% o. w. f. In a dye bath with a bath ratio of 1:20 and 2% o. w. f. When the density of 6-nylon jersey is APA and the density of unsilqueted cotton knit is AC,
Synthetic polyamide fiber with one bath system using HN dye with NPA / NC of 200% or more, APA / AC of 200% or more, APA / NPA of 80-200% and each correction color difference of 5.0 or less A method for dyeing a composite material, characterized in that the composite material containing selenium is subjected to dip dyeing, and alkali reduction is carried out after dip dyeing (claim 1)
Is achieved.

  As a result of intensive studies, the inventor has determined that the nylon and cotton composite material is dyed under predetermined conditions, the ratio of the nylon concentration to the cotton concentration, and the case where the nylon is dyed under acidic conditions and neutral conditions. Dyeing with a dye having a density ratio within a predetermined range, i.e., using the HN dye, or using HN dye in combination with a different dye (alkali reducing dye), followed by alkali reduction. As a result, the present inventors have found that the above problems can be achieved and completed the present invention.

  The combination of dyeing with a disperse dye and alkali reduction has been conventionally performed in dyeing polyester or a composite material containing polyester.

  For example, in the dyeing of polyester or polyester / cellulose composite material, after dyeing the polyester side with disperse dyes, by alkaline reduction washing with caustic soda and hydrosulfite, etc. The disperse dye adhering in the cellulose fiber is reduced and decomposed and removed by subsequent washing (reduction cleaning). This is because the disperse dye diffused into the polyester fiber at high temperature and solidified by the temperature drop and dyed in the polyester fiber is not decomposed at all below 100 ° C. even by a strong alkaline reducing action. Undyed dyes are based on being easily decomposed and removed by a cleaning agent in the same bath.

  Also, in dyeing composite materials containing polyester such as polyester / cellulose composite materials, a composite dye containing a disperse dye and a reducing dye is used, and the polyester side is subjected to high-temperature dyeing at around 130 ° C or thermosol at 180 ° C to 220 ° C. After dyeing with normal dyeing methods such as dyeing, alkali reduction with caustic soda and hydrosulfite etc. is performed to dye the reducing dye on the cellulose fiber and at the same time disperse the undyed material adhering to the polyester fiber surface There is also a method in which disperse dyes adhering to dyes and cellulose fibers are reduced and decomposed and removed by washing.

  This method is a very effective method in which reduction washing is performed simultaneously with the dyeing of the reducing dye, and as a rational dyeing method for improving various fastnesses such as sublimation and wetness, a 100% polyester material is used. Has been widely used for continuous dyeing of composite fiber materials of polyester and cellulose fibers, and has contributed to the great development of these dyeing fields.

  On the other hand, a dyeing method in which synthetic polyamide fiber is dyed by an ionic bond in an acidic bath using an acid dye or an acid-containing metal dye, or a composite fiber material composed of synthetic polyamide fiber or synthetic polyamide fiber and cellulose fiber, In the dyeing method for dyeing with a reactive dye having a sulfonic acid group, no examples of dyeing with a combination with an alkaline reducing agent or with a reducing dye have been found. This is because these water-soluble dyes are thought to be easily decomposed by a general reducing agent.

  However, as a result of the study of the present inventors, acidic metal-containing dyes dyed on synthetic polyamide fibers, disperse dyes and reactive dyes, and some acidic dyes are (degradation of the dye is recognized in the acidic reduction action, It was found that, contrary to expectations, there was little degradation for alkaline reduction in alkaline baths.

  Therefore, the above-mentioned dye, which has a high dyeing power on synthetic polyamide fibers and a small dyeing power on other than synthetic polyamide fibers, is mixed with an alkali-reducing dye, so that dip dyeing and alkali reduction are carried out in a one-bath system. It was found that the synthetic polyamide / cellulose composite material can be dyed in the same color or in a clear different color. Further, by combining dyeing dyeing with the dye and alkali reduction, the synthetic polyamide / cellulose composite material is dyed, and if the dye on the cellulose side is discharged, that is, by removing the dye contaminated or dyed on the cellulose fiber, The present inventors have found that it is possible to clearly stain a white area and have reached the present invention.

  The composite material containing the synthetic polyamide fiber to be dyed by the dyeing method of the present invention includes synthetic fiber such as polyacryl, polyester (including cationic dyeable polyester), cellulose fiber, and the like together with synthetic polyamide fiber. It is a composite material. Especially, the dyeing | staining method of this invention is used suitably for the composite material which contains a cellulose fiber with a synthetic polyamide fiber. Claim 2 corresponds to this preferable mode.

  The dyeing method of the present invention is characterized by using the above-mentioned HN dye. HN dye exhibits a large dyeing power on synthetic polyamide fibers, while the dyeing power on these fibers is small even if cellulose fibers or the like are present in the same bath. And the HN dye adhering to a cellulose fiber etc. is easily removed by alkali reduction. In other words, this feature of the HN dye works very advantageously to make the cellulose fiber portion or the like clear white (outlined) or to dye the cellulose fiber portion or the like in the same color or a clear different color. The present invention has found that HN dyes dyed on synthetic polyamide fibers with high dyeing power are not removed by alkali reduction, and that HN dyes adhering to other fibers are easily removed by alkali reduction. Has been completed.

  The dyeing method of the present invention is a dyeing method in which dyeing is performed by a one-bath system. In dyeing using a mixture of HN dye and alkali-reducing dye, as long as it is a one-bath method, a method in which HN dye and alkali-reducing dye are mixed and added to the dyeing bath may be used. Any of the methods of adding an alkali-reducing dye and carrying out reduction dyeing after the dyeing is performed is included. Since it is a one-bath system, high productivity can be obtained. Dipping means a dyeing method in which an object to be dyed is immersed in a dye bath in which the dye is dissolved or dispersed, and the dye is adsorbed to the object to be dyed and fixed, and includes exhaust batch dyeing and continuous dyeing. It is.

  In the dyeing method of the present invention, alkali reduction is performed after dip dyeing. Alkaline reduction means reduction performed under alkalinity. Usually, it is carried out using an alkaline agent that makes the dyeing bath alkaline and a reducing agent that performs a reducing action under alkaline conditions. Alkaline reduction is preferably performed by reducing the potential (−mV) in an alkaline agent having a pH of 9.0 to 12.5 at 20 ° C. and an alkaline bath thereof, ie, a bath having a pH of 9.0 to 12.5 at 20 ° C. ) Is carried out using a reducing bath containing a reducing agent exhibiting 300-1200. Claim 3 corresponds to this preferable mode.

  After alkali reduction, washing with a detergent or the like is performed in the same manner as in normal dyeing. By this alkali reduction and washing, HN dye adhering to fibers other than the synthetic polyamide fiber, for example, cellulose fiber is removed. On the other hand, the HN dye dyed on the synthetic polyamide fiber is not removed and is hardly affected.

  One aspect of the dyeing method of the present invention is a method for dyeing a composite material characterized in that an alkali reducing dye is used in combination with an HN dye. Claim 4 corresponds to this aspect. Here, “hybridized” means that two or more kinds of dyes are used together, and includes a method of adding an alkali-reducing dye after the synthetic polyamide fiber is dyed with HN dye. It is not limited to the system which mixes a reducing dye and adds to a dyeing bath.

  Here, the alkali-reducing dye is insoluble in water before alkali reduction, but is reduced under alkalinity to become soluble in water, dyed on fibers such as cotton, and then oxidized by an oxidizing agent. It is a dye that becomes insoluble in water and adheres to the fiber. Examples of the alkali-reducing dye include vat dyes, sulfur dyes and indigo dyes. Claim 5 corresponds to this embodiment, and is a method for the same color dyeing or different color dyeing of a composite material characterized by using an alkali reducing dye in combination with the HN dye, wherein the alkali reducing dye is a vat dye. And a dyeing method characterized by being selected from sulfur dyes and indigo dyes.

  According to the dyeing method of the aspect of claim 4, the composite material can be dyed in the same color or different colors. The synthetic polyamide fiber side is dyed with HN dye. On the other hand, the side other than the synthetic polyamide fiber, for example, the cellulose fiber side is not dyed so much by the HN dye, and the HN dye on the side of the cellulose fiber or the like is almost removed by alkali reduction and washing after the dyeing.

  When the composite material is dyed in the same color, the HN dye and the alkali reducing dye having the same hue are used, and both are mixed and dyed. Since the HN dye adhering to the cellulose fiber side is removed by alkali reduction and washing, the cellulose fiber side is dyed only with the alkali reducing dye. Therefore, when an alkali reducing dye having the same hue as that of the HN dye is used, a composite material in which the synthetic polyamide fiber side and the cellulose fiber side are dyed in the same color can be obtained.

  When each of the fibers constituting the composite material is dyed in different colors, HN dyes and alkali reducing dyes having different hues are used, and both are mixed to perform dyeing. Claim 6 corresponds to this aspect, and is the dyeing method according to claim 4, wherein the hue of the alkali-reducing dye is different from the hue of the HN dye, and the synthetic polyamide fiber and other fibers are dyed differently. A dyeing method characterized by the above is provided.

  As in the case of the same color, the HN dye adhering to the cellulose fiber side is removed by alkali reduction and washing, so that the cellulose fiber side is dyed only with the alkali reducing dye. As the alkali-reducing dye, those that hardly dye synthetic polyamide fibers are desirable. If such an alkali-reducing dye is used, the synthetic polyamide fiber side and the cellulose fiber side are dyed by only one of the HN dye and the alkali-reducing dye, respectively. The density and the like can be easily adjusted, and the hue of the synthetic polyamide fiber is not affected by the alkali reducing dye, so that a clearer different color can be obtained.

  The dyeing method of claim 4 can also be suitably applied to a method of dyeing a composite material containing synthetic polyamide fibers in a camouflage color by a one-bath system. A seventh aspect corresponds to this aspect, and provides the method for dyeing a composite material according to the fourth aspect, characterized in that camouflage color dyeing is obtained.

  Camouflage color is a color that is widely applied to uniforms of military uniforms and rangers, and uses shades of Green, Brown, Khaki, Gray, or Olive, and is stray light for photographs taken with an infrared camera. Is an important feature. In addition, for military uniforms and uniforms of rangers, it is required that all solidity is excellent. Conventionally, however, dyes with the above hues are used, and composite materials such as synthetic polyamide / cellulose, which are superior in functionality, weight reduction, and durability, are dyed in a camouflage color by a one-bath system, and high fastness is obtained. No method has been found.

  As a result of the study, the present inventor determined that a dye having a hue of Green, Brown, Kaki, Gray or Olive and having a characteristic of being stray light with respect to a photograph taken by an infrared camera is an HN dye and an alkali reducing dye. When the dyeing method according to claim 4 is used, a composite material such as synthetic polyamide / cellulose can be easily dyed in a camouflage color by a one-bath method, and all dyeings are excellent in fastness. It was found that can be obtained. According to the present invention, uniforms of military uniforms and rangers using composite materials such as synthetic polyamide / cellulose can be dyed in camouflage color with excellent productivity.

  8. The dyeing method according to claim 7, wherein the composite material containing the synthetic polyamide fiber further contains at least one fiber selected from synthetic fibers other than the synthetic polyamide fiber, and further synthesized other than the HN dye and the alkali reducing dye. When dyeing is performed using a dye for fibers, a camouflage color composed of multiple colors can be obtained, which is preferable.

  The dyeing method of the present invention can also be applied to white leaving dyeing of composite materials. Claim 8 corresponds to this aspect.

  That is, if a composite material containing a synthetic polyamide fiber, for example, a composite material containing a synthetic polyamide fiber and a cellulose fiber is dyed by a combination of dip dyeing with HN dye and alkali reduction, the fiber is contaminated or dyed. The dye can be easily removed by alkali reduction (discharging) to obtain a dyed product in which only the synthetic polyamide fiber side is dyed (white leaving dyeing). By this method, a clear white-remaining dyeing can be obtained.

  In the ninth aspect of the present invention, there is provided a composite material containing a synthetic polyamide fiber dyed by the dyeing method. This composite material has the excellent characteristics of a composite material containing synthetic polyamide fiber, and the multiple materials constituting the composite material are dyed in the same color, in a clear different color, and in clear white residue. Fastness is also achieved and it has high added value.

  According to the method for dyeing a composite material of the present invention, a composite material containing synthetic polyamide fibers can be dyed in the same color, in a clear different color, or in a clear white residue with a high productivity of a one-bath system. This dyeing method can be applied to a wide variety of dyeing dyeings, and not only helps to streamline dyeing, saves energy and improves quality, but also features clear water-soluble dyes and robust, camouflage reducing properties. It is intended to fully exhibit the characteristics of the dye, and provides a dyeing process with functionality, durability and fashionability.

  Therefore, the composite material of the present invention obtained by this dyeing method is a composite material in which a plurality of materials constituting the composite material are dyed in the same color, in a clear different color, or in a clear white residue. It can be used to produce products with high added value.

  The HN dye is well dyed on synthetic polyamide and is an alkali for 15 minutes at a bath ratio of 1:20 at a temperature of 60 ° C. containing 40 ° Be ′ caustic soda 15 ml / l and hydrosulfite 5 g / l as a reducing agent. It is a water-soluble dye selected from acidic dyes, acidic metal-containing dyes, disperse dyes, and reactive dyes that can withstand reducing conditions. In the past, it was thought that all of these water-soluble dyes were decomposed by alkali reduction, but the present inventor considered that these dyes dyed on synthetic polyamide were not decomposed by alkali reduction. It has been found that it can be used effectively as an HN dye. Further, as the disperse dye, those that are dyed well on the synthetic polyamide fiber and are robust are preferably used. The following dyes are preferably exemplified as such HN dyes.

  Sumifix Yellow 2GL, Sumifix Yellow GR, Sumifix Golden Yellow GG, Sumifix Brill Red G, Sumifix Brill Red 7BF, Sumifix Supra Brill Red BSF, Sumifix Supra Rubine Red E-XF, Sumifix Brill Red BB, Sumifix Supra Brill Red GF, Sumifix Brill Orange 3R, Sumifix Bill Blue R, Sumifix Bill Orange GRS, Sumix Turq Blue G (n), Sumifix Super Blue BRF, Sumifix BlackBl Black E-XF, Sumifix Black EX, Sumifix Supra Scallet 2GF, Realan Yellow G, Realan Red Yellow, RC, Realan Red G, Realan Red G, Realan Red G, Realan Red G, Realan Red G. ReaNova Navy CA, Realan Blue RC, Realan Black G, Cibacron Yellow H-2G, Cibacron Orange C-3R, Cibacron Yellow F4G, Cibacron Yellow C-R, Cibacron C-2 l Bv Yellow 3G, Lanyl Yellow G, Lanyl Yellow GR, Lanyl Orange R, Lanyl Red B, Lanyl Blue 3G, Lanyl Blue Blue G, Lanyl Blue G , Sumikaron Turquoise Blue S-GL, Sumikaron Turquoise Blue 76, Sumikaron Blue S-BBL, Sumikaron Yellow E-RPD, Sumikaron Red E-RPD, Sumikaron Red E-RPD, mikaron Blue E-FBL, Sumikaron UL Blue GF, Sumikaron Brill Red S-BLF, Sumikaron Brill Pink SE-RL (n), Miketon Polyester Red 2BSF and Kayalon Polyester Blue KSF, Telon Turquoise M-GGL, Suminol Milling Brill Green 5G.

  As described above, the alkali-reducing dye can be easily selected from vat dyes, indigo dyes, sulfur dyes, and the like. However, since it is used for hybrid dyeing with a water-soluble HN dye, Water-dispersible and water-soluble reducing dyes are desirable. By using the dye of such a form, various dyeing dyeing including a continuous type becomes possible.

  At high temperatures, dyeing of reducing dyes on synthetic polyamides tends to occur, and in the case of white residue dyeing or different color dyeing, it is desirable that there is less dyeing of alkali reducing dyes on synthetic polyamides. Is preferably a vat dye capable of low-temperature dyeing (40-70 ° C.).

  Also in the case of camouflage color dyeing, a vat dye having a hue such as Brown, Olive, Green and Gray and having infrared reflection characteristics is preferably used. When dyeing synthetic polyamide fiber and cellulose fiber to the same color, C.I. I. Vat dyes such as Vat Green 1 are suitable for obtaining the most robust and durable dyeings because they dye the synthetic polyamide fibers and cellulose fibers substantially the same color and fast. A dyed composite material of synthetic polyamide fiber and cellulose fiber obtained by such a method is lightweight and excellent in hygroscopicity and drying properties, and is thus very useful for improving the functionality of uniforms such as military uniforms.

  On the other hand, sulfur dyes are known as dyes that dye cellulose fibers most deeply among Green, Navy, and Black dyes, and are suitably used for applications in which the cellulose fiber side is dyed deeply. The indigo dye is preferably used for jeans-like blue dyeing of a composite material (which may contain polyacryl and polyester) composed of synthetic polyamide fiber and cellulose fiber.

  As the vat dye, the following dyes are preferably exemplified. C. I. Vat Yellow 2, Vat Yellow 33, Vat Orange 9, Vat Orange 15, Vat Orange 2, Vat Red 10, Vat Violet 13, Vat Blue 6, Vat Blue 14, Vat Blue 64, Vat Blue 64, Vat Green 64, Vat Green 64 13, Vat Black 25, Vat Black 27, Vat Brown 1, Vat Brown 3, Vat Brown 68, Vat Brown 72, Vat Blue 72, Vat Black 8, Vat Black 9, MikethroneG . Green FFB 1, Red F3B, Brown GGS, Brown BR, Olive MW (manufactured by Dystar), Brown GS, Brown 5RN, Brown RP, Gray CL, Direct Black RB.

  As the indigo dye, the following dyes are preferably exemplified. Mitsui Indigo Pure Exn (manufactured by Dystar).

  As the sulfur dye, the following dyes are preferably exemplified. C. I. Sol. Sulfurfur Yellow 24, C.I. I. Sol. Sulfur Fur Orange 1, Sol. Sulpfur Blue 2, Sol. Sulpfur Blue 5, Sol. Sulpfur Blue 7, Sol. Sulpfur Blue 15, Sol. Sulfurfur Red 2, Sol. Sulpfur Brown 12, Sol. Sulfurfur Brown 52, Sol. Sulfurfur Brown 52, Sol. Sulpfur Brown 97, Sol. Sulpfur Green 3, Sol. Sulfur Fur Black 1, C.I. I. Sol. Sulpfur Green 14, Sulpfur Green 3, Kayaku Homodye Yellow GNF-S, Orange 2RF-S, Red Brown RF-S, Blue RBL-S, Olive KL-S, Olive Bck-Lck As mentioned above, Kayaku Homodye (manufactured by Nippon Kayaku Co., Ltd.).

  As the alkali agent used for alkali reduction, an alkali agent having a pH of 9.0 to 12.5 at 20 ° C. is preferably selected. Here, an alkaline agent having a pH of 9.0 to 12.5 at 20 ° C. means an alkaline agent having an aqueous solution having a concentration of 1% by weight or more of the alkaline agent and having a pH of 20 ° C. within this range. As the reducing agent used for the alkali reduction, a reducing agent exhibiting a reduction potential (−mV) in a predetermined range as described above is preferable.

  Furthermore, based on the type of dye used, in particular the ease with which the dye is reduced, the concentration of the dye at the time of dyeing, the dyeing temperature that is set, and the like, the type and amount of alkali agent and reducing agent are selected.

  For example, a vat dye is converted from an oxidized form to a reduced form by reduction, and becomes an Na-leuco form, for example, an alkali in the same bath, dissolved in water, and quickly dyed on cellulose fibers. However, it becomes an oxidant again and solidifies in the fiber as it is to form a strong dyeing. The reduction potential of the Na-leuco body at this time is about 400 to 1100 (-mV), and the larger this value, the more difficult the reduction, while the dye of 600 (-mV) or less is easy to reduce. Therefore, the type and amount of the reducing agent are selected in consideration of the reducibility, the dyeing temperature, the amount of alkali used, and the like.

  More specifically, for refractory vat dyes, hydrosulfite, thiourea dioxide, or sodium borohydride, which is a reducing agent having a reduction potential higher than the reduction potential of the leuco form of the dye, is generally caustic. Used in alkaline bath. The standard dyeing conditions in this case are as high as 55 to 70 ° C., the amount of reducing agent is 5 to 25 g / l for hydrosulfite, the amount of caustic soda is 5 to 25 g / l, and the dyeing time is 30 to 60. About minutes.

  Hydrosulfite is also used for easily reducible vat dyes or indigo dyes. However, in this case, caustic soda is 2.5 to 12.5 g / l (about half that of the hardly reducing vat dye), the temperature is 40 to 55 ° C., and sodium sulfate is 20 g / l. Conditions are suitable. In addition, since this type of dye has good levelness, it is also used for light color dyeing. Therefore, sodium carbonate as a weak alkaline agent, acidic sodium sulfite, sodium sulfite, or glucose (D-glucose) as a weak reducing agent. ) Etc. can also be used.

  When a high dyeing temperature of about 80 to 95 ° C. is employed as necessary, a reducing agent such as redol C (zinc formaldehyde sulfoxylate) that is more stable than hydrosulfite (sodium hydrosulfite) is used. it can. In addition, the dye conditions using these chemical | medical agents are preferably applicable also to the dyeing | staining which uses the sulfur dye which requires comparatively high temperature (80-100 degreeC).

  For dyeing using sulfur dyes, sodium sulfide and sodium hydrosulfide generally used for dyeing sulfur dyes can also be used as reducing agents. However, the method of dyeing at a high temperature (80 to 100 ° C.) has a problem of breathing. Therefore, a method of using caustic soda and hydrosulfite is preferably used in the same manner as the reduction dyeing of the vat dye, using a dye of the type that is recently decomposed or dissolved in water as a sulfur dye.

  Next, the same color dyeing in the dyeing method of the present invention, that is, the hybrid dyeing method in which the synthetic polyamide fiber side and the other material side are dyed in the same hue will be described more specifically with a preferred embodiment. The same color dyeing | staining of this invention is not limited to this aspect, A various change is possible in the range which does not impair the meaning of this invention.

  In this embodiment, a hybrid dye of a Green HN dye comprising a disperse dye, an acidic metal-containing dye and a clear reactive dye and a Green vat dye as a reducing dye is used. More specifically, Green HN dye is C.I. I. Disperse Blue 60, C.I. I. Acid Blue 127, C.I. I. This dye is composed of Reactive Yellow 37 and reactive dye Realan Yellow G (manufactured by Dystar). As a vat dye, although it is the same color and slightly dyed on synthetic polyamide fiber during reduction dyeing, it has good fastness. . I. Vat Green 1 is used.

  First, using the mixed dye of Green HN dye and vat dye, dyeing is carried out at 95-100 ° C. for about 40 minutes in a dye bath containing sodium sulfate, 1% acetic acid / 1% sodium acetate (1/1) acid. The temperature is then cooled to 60 ° C. By the first stage dyeing, most of the Green HN dye is dyed on the synthetic polyamide fiber side. Even if it is slightly dyed on the cellulose fiber side or a little dye remains in the dye bath, it is decomposed and removed at the next second stage of reduction dyeing, so there is almost no influence.

  The sodium sulfate used in the first stage dyeing is effective for improving the dyeing of the reactive dye in the dyeing bath, and the addition amount is preferably 20 to 50 g / l. If it is more than that, there is a possibility that the dispersibility of the disperse dye in the dyeing bath is deteriorated. The acid added to the bath is effective in promoting the dyeing of the reactive dyes and acid dyes contained, and the stability of the disperse dyes. The acid side consisting of 1% acetic acid / 1% sodium acetate (1/1) ( As a buffer solution of PH 4.0 to 5.5), it is preferable to use 5 to 15 g / l.

  In the case of using a vat dye, the dyeing temperature is usually 40 to 70 ° C. I. Since Vat Green 1 is a hardly-reducing dye, a relatively high dyeing temperature of about 60 ° C. is suitable as the second stage dyeing temperature.

  Then add hydrosulfite 5-20g / l, reduce the alkali for 20-40 minutes, add water while draining (overflow if necessary), wash with water, add about 50% acetic acid. When neutralized and sufficiently washed with water, the vat dye in the fiber is oxidized and dyed as it is. Finally, the same color dyeing is completed by soaping with neutral detergent (1 to 2 g / l) or the like (at 80 to 100 ° C. for 5 to 15 minutes). When the above-described neutralization and oxidation by washing alone are insufficient, the dye in the fiber can be completely oxidized with a commercially available oxidizing agent such as hydrogen peroxide (about 3 g / l).

  Depending on the structure of the dyeing machine, the problem that occurs during this second stage of reduction dyeing is that the reducing dye comes into contact with air during dyeing and an oxide film of the dye forms and adheres to the fiber material. There is a case. In this case, it is preferable to use a commercially available protective colloid agent as an oxide film inhibitor.

  In recent years, the use of dispersed or water-soluble reducing dyes has become common. From the first stage of dyeing, the reducing or water-soluble reducing dye can be dyed together with HN dye in one bath, and dyeing can be advantageously performed. In the above embodiment, it is possible to add Vat Green dye from the first stage of dyeing, which does not adversely affect the dyeing of the HN dye on the synthetic polyamide fiber.

  Of the reducing dyes, vat dyes and sulfur dyes are similar in oxidation-reduction conditions and dyeing on synthetic polyamide fibers and cellulose fibers, and there are relatively many combinations in which the combined use is allowed. For example, the C.I. I. Vat Green 1 is a C.I. I. Sol. Since Sulfur Green 3 is relatively similar in dyeability and hue, both can be used in combination.

  Next, the remaining white dyeing in the dyeing method of the present invention will be described. In white-remaining dyeing, an alkali-reducing dye (CI Vat Green 1 in the above embodiment) is not used. However, other conditions are the same as the above-mentioned same color dyeing. That is, as the HN dye, those similar to those described above are used, and the conditions for alkali reduction, oxidation, washing and other conditions are the same as described above.

  Next, the different color dyeing in the dyeing method of the present invention will be described. In the different color dyeing, an alkali reducing dye having a hue different from that of the HN dye is used. For example, since the Green HN dye is used in the above-described embodiment, the alkali-reducing dye having a hue other than Green is used. Other conditions are the same as the above-mentioned same color dyeing. That is, as the HN dye, those similar to those described above are used, and the conditions for alkali reduction, oxidation, washing and other conditions are the same as described above. In addition, if an alkali-reducing dye that is dyed on a synthetic polyamide fiber at the time of reduction dyeing is used, the synthetic polyamide fiber side has a hue different from that of the HN dye. Preferably used.

  White-stain dyeing and different-color dyeing are conventionally performed in the printing field, and are advanced techniques for obtaining high-quality dyed products with a wide variety of patterns (patterns) and the sharpness of the patterns. In other words, on a dyed cloth (ground dyeing) that has already been dyed, the pattern pattern is printed with a discharge paste containing a skillfully prepared reducing agent or a colored discharge paste containing a dye pigment that is resistant to the reducing agent. By printing, drying, steaming and other heat treatments, the background dye is sharply reduced and decomposed into white patterns (outlined) according to the outline of the patterned pattern, or at the same time as the whited pattern, the dye in the reducing paste is patterned. It is said that it is a printing method for obtaining a sharp pattern. However, problems such as pattern smearing, white ground contamination, and insufficient whiteness often occur.

  On the other hand, the white residue dyeing or the different color dyeing by the method of the present invention is a method by dip dyeing of a composite material composed of various fibers, and cellulose fibers in a dye bath having a weight of at least about 3 times the weight of the object to be dyed. This is a method of white or white coloring the sides. That is, it differs from the conventional method in that it is a method by dip dyeing rather than textile printing. And the big advantage that dyeing | staining can be achieved by one bath system is acquired.

  Examples of the composite fiber material to be dyed by the dyeing method of the present invention include composite materials such as synthetic polyamide / cellulose blend, union, pattern, and reversible, and these composite materials include alkalis such as polyester and polyacryl. Examples include composite materials that further include fibers that can withstand reduction. According to the dyeing method of the present invention, a characteristic high degree of dyeing of a composite material containing such a wide variety of fibers can be obtained.

  A typical example of the cellulose fiber contained in the composite fiber material is cotton, but the dyeing method of the present invention is also suitable for regenerated fibers such as rayon such as cupra with high water absorption and tencel. Applicable to. Preferred examples of the polyester fiber include a cationic dye-dyed modified polyester and a polytrimethylene terephthalate-based polyester fiber that can be dyed at normal pressure. On the other hand, in the case of a material containing natural polyamide fibers such as wool, care must be taken because these fibers generally cannot withstand strong alkali, and dyes dyed on these fibers are easily decomposed by a reducing agent. Silk may be applied by using sodium carbonate.

  next. An application to the case of dyeing camouflage colors in the manufacture of military uniforms will be described.

  Conventionally, camouflage color dyeing has been carried out by a printing method using a reactive dye, a vat dye or the like on a cotton cloth or a direct printing method on a part of a pigment. Since the camouflage color is stray light with respect to the infrared camera, the vat dyes Green, Olive and Brown dyes having camouflage color properties are mainly used for this dyeing. Further, it is processed by dyeing and printing mainly using a reactive dye of a neutral color.

  The dyeing method of the present invention, that is, a method using a hybrid dye of an HN dye and a reducing dye is suitable as a method for dyeing a composite material composed of synthetic polyamide fiber and cotton in a camouflage color. For example, if the vat green, olive, and brown dyes are used as the reducing dye and the HN dye is used as the intermediate reactive dye, the same camouflage color as that obtained by the conventional printing method or the direct printing method can be obtained. Can be obtained.

  In addition, the present invention is not based on the textile printing method, but is a method in which camouflage color processing is performed by one bath type dyeing by skillfully using a composite material composed of various fibers, and excellent productivity is achieved. In addition, by adding moderately synthetic fibers such as synthetic polyamide to military uniforms that have been mainly made of cotton, it is possible to improve functionality and improve light resistance by adding flexibility, stretchability, lightness, etc. Is done. The reduction in water absorption and sweat absorption due to the inclusion of synthetic fibers can be dealt with by combining with rayon having extremely high water absorption. The cold can be dealt with by appropriately containing polyacrylic fibers. The method of the present invention can also be applied to composite materials containing multiple fibers such as synthetic polyamide, rayon, polyacrylic fiber, and to obtain camouflage (polychromatic) products having excellent properties with high productivity. Can do. In addition, the inclusion of polyester fibers is preferable because the durability of the product is improved and the polychromaticity of the camouflage pattern is also given.

  As described above, it is necessary to use a dye having a hue of Green, Olive, Brown, Gray, or Kaki and having high reflection in the near infrared region for the camouflage color dyeing process. Therefore, the HN dye used for dyeing on the synthetic polyamide fiber side of the present invention is mainly selected from dyes having these hues. As this dye, C.I. I. Preferable examples include acidic metal-containing dyes such as Acid Yellow 116, Brown 19, 28, 226, 297, Black 60, 50, Lanyl Olive BG, Lanyl Khaki G (manufactured by Sumitomo Chemical Co., Ltd.). The improvement of wet fastness and the adjustment of hue can be handled by using reactive dyes of the three primary colors belonging to the HN dye.

  Examples of vat dyes for dyeing cellulose fibers in camouflage colors include C.I. I. Vat Orange 2, C.I. I. Vat Brown 1, 3, 68 and 72, C.I. I. Vat Green 1, 3, and 13, C.I. I. Vat Black 8, 25, 27 and the like are preferably exemplified.

  When the composite material contains polyester fiber, preferably, in addition to the HN dye and the alkali-reducing dye, a disperse dye that directly dyes the polyester fiber is added, and the polyester fiber is dyed with the disperse dye. . Such disperse dyes include, for example, Sumikaron Yellow Brown S-2RF, Sumikaron Yellow Brown S-BRF, Sumikaron Blue S-3RF, Sumikaron Blue SE-RPD, Sumikaron Blue E-RPD, Sumikaron Blue E-RPD, Sumikaron Blue E-RPD. SE-RPD, Sumikaron Red E-RPD, Sumikaron Red SE-RPD, Sumikaron Rubin SE-GL, Sumikaron Bordeaux SE-BL, Sumikaron Navy Blue S-GL (manufactured by Sumitomo Chemical Co., Ltd.)

  As the cationic dye for dyeing the polyacrylic fiber, an intermediate color dye such as Brown or Olive is not overcoated. Therefore, when the composite material contains polyacrylic fibers, dark-colored three primary color dyes are used instead.

  Examples of such dyes include C.I. I. Basic Yellow 32, C.I. I. Basic Yellow 28, C.I. I. Basic Orange 30, C.I. I. Basic Red 18, C.I. I. Basic Blue 41 etc. are mentioned. However, when an anionic dye such as an acid dye or a disperse dye containing an anionic dispersant is used in one bath, it is necessary to prevent precipitation. Therefore, in this case, it is preferable to use a dispersed cationic dye for safety. As this dye, Estrol Yellow 3RL-SD, Estrol Red GSL-SD, Estol Blue GSL-SD, Estol Navy Blue 3RL-SD (manufactured by Sumitomo Chemical Co., Ltd.) and the like are suitable.

Example 1
Table: 6% of reversible composite material consisting of 60% nylon and back: 40% cotton pile. After dewatering by wetting with hot water, Sumikaron Turq. 23.8 parts of Blue S-GL 200% (manufactured by Sumitomo Chemical Co., Ltd.), Lanyl Bill. 23.8 parts of Blue G e / c (manufactured by Sumitomo Chemical Co., Ltd.), 26.2 parts of Sumifix Yellow 2GL 150% (manufactured by Sumitomo Chemical Co., Ltd.), and 26.2 parts of Realan Yellow G (manufactured by Dystar). Green HN dye (NPA / NC: 460, corrected color difference: 4.73, APA / AC: 530, corrected color difference: 4.30, APA / NPA: 105, corrected color difference: 3.70) 0.84% o . w. f. To 100 ml of the dyebath (bath ratio 1:20). Next, after adding 3 g of sodium sulfate at room temperature and staining for 5 minutes, 0.7 ml of 1% acetic acid aqueous solution and 1% sodium acetate aqueous solution 1: 1 buffer solution (PH 4.0 to 5.5) was added. Then, the temperature was raised to 95 to 100 ° C. and dyed for 40 minutes.

  Next, after cooling the temperature of this dye bath to 60 ° C., Mikethrene Brill. Green FFB 1. 4% o. w. f. Then, 2.2 ml of 40 ° Be ′ caustic soda and 1 g of hydrosulfite as a reducing agent were added and dyed for 20 minutes. After draining, washing with water, neutralizing with acetic acid (3 ml / l), and washing with water, the dye was oxidized and dyeing was completed. Finally, it was washed with water and finished with normal soaping. The dyed product obtained has the same color on the front and back sides and a clear green color. The fastness cleared light resistance and chlorine, grade 5, and the best green dyeing was obtained.

Example 2
After 5 g of the same reversible composite material as in Example 1 was wetted with hot water and dehydrated, 50 parts of Sumifix Black EX conc (manufactured by Sumitomo Chemical Co., Ltd.), 20 parts of Aminyl Black F-GL (manufactured by Sumitomo Chemical Co., Ltd.), Black HN dye (NPA / NC: 238, correction color difference: 2.47, APA / AC: 214) consisting of 10 parts of Lanyl Gray BG e / c (manufactured by Sumitomo Chemical Co., Ltd.) and 20 parts of ReaNova Navy CA (manufactured by Dystar) , Corrected color difference: 3.42, APA / NPA: 208, corrected color difference: 2.36) 7.0% o. w. f. To 100 ml of the dyebath (bath ratio 1:20). Then, after 40 minutes under the same conditions as in Example 1, the temperature was cooled to 60 ° C., and 2.2 ml of 40 ° Be ′ caustic soda and 1 g of hydrosulfite as a reducing agent were added and dyed for 20 minutes. Finally, a post-treatment similar to that in Example 1 was performed for finishing.

  As a result, the 6-nylon side of the table was a thick black, and the back cotton pile side was discharged with a reducing agent to become pure white. And the influence of decomposition | disassembly etc. of the dye dye | stained to the 6-nylon side was not seen at all.

Example 3
After wetting 0.4 g of polyester processed fabric, 0.6 g of cotton knit, 0.6 g of 6-nylon and 0.4 g of polyacrylic cloth with hot water to remove the liquid, Red HN dye consisting of reactive dye (NPA / NC: 226, corrected color difference: 2.61, APA / AC: 430, corrected color difference: 2.39, APA / NPA: 140, corrected color difference: 1.16) 0.5% o. w. f. Add to 40 ml of dye bath. Next, 0.5 ml of the above-mentioned buffer material on the acidic side and Ionette FY-104 (manufactured by Sanyo Kasei Co., Ltd.) which is a precipitation inhibitor are added and dyed at 60 ° C. for 10 minutes.

  In this dye bath, Astrazon Blue AU (Dystar) 0.4% o.d. w. f. Then, the temperature is raised to 95 to 100 ° C., dyed for 30 minutes, 1.2 g of sodium sulfate is added and dyed for another 10 minutes, and then cooled to 60 ° C. Finally, Mikethrene Yellow 3GL (Vat dye manufactured by Dystar) 1% o.d. w. f. Then, 1 ml of 40 ° Be ′ caustic soda and 0.5 g of hydrosulfite were added and dyed for 20 minutes. After draining, the same post-treatment as in Example 1 was performed for finishing.

  As a result, 6-nylon was red, polyacryl was blue, and cotton knit was yellow. The dye slightly contaminated with the polyester was reduced and decomposed at the time of dyeing the vat dye to improve the whiteness of the polyester, and a good whitening result was also obtained.

Example 4
Two pieces of normal pressure dyeable polyester knitted fabric 4 cm ² , 2 pieces of cotton knit 4 cm ² , 2 pieces of 6-nylon jersey 4 cm ^2, and 2 pieces of polyacrylic cloth 4 cm ² , a total of 8 pieces were randomly sewn together, An article to be dyed having a width of about 8 cm and about 5 g was prepared. The dyed object consisting of these four types of fibers is moistened with hot water, drained,
Sumikaron Yellow Brown S-BRF (Sumitomo Chemical Co., Ltd.) 0.4% o. w. f. , Sumikaron Navy Blue S-GL (Sumitomo Chemical Co., Ltd.) 0.1% o. w. f. ,
Mikethrene Olive MW (Dystar Co., Ltd. vat dye) for dyeing cotton 0.2% o. w. f. , Mikethrene Brown BR (Dyster Vat Dye) 0.8% o. w. f.
Lanyl Khaki G (manufactured by Sumitomo Chemical Co., Ltd.) 0.2% o. w. f. Yellow HN dye (NPA / NC: 516, corrected color difference: 3.95, APA / AC: 581, corrected color difference: 2.25, APA / NPA: 109, corrected color difference: 1.20) 0.2% o. w. f. , And Estrol Yellow 3RL-SD (Sumitomo Chemical Co., Ltd.) 0.2% o. w. f. Estrol Blue GSL-SD (manufactured by Sumitomo Chemical Co., Ltd.) 0.2% o. w. f.
In a 100 ml dyebath containing

  Next, 0.7 ml of the acidic buffer solution used in Example 1 was added, the temperature was raised, dyed at 95-100 ° C. for 40 minutes, and then cooled to 60 ° C. Subsequently, 2.2 ml of 40 ° Be ′ caustic soda and 1 g of hydrosulfite are added and dyed for 10 minutes, then 3 g of sodium sulfate is added and dyed for 30 minutes and drained. The same post-treatment as in Example 1 was performed for finishing.

  The result is that the polyester side is dyed in an olive color, the cotton side is a dark blue brown color, the nylon side is a yellow khaki color, and the polyacryl side is a green color. A dyed product having a color tone forming a color was obtained.

Example 5
6 g of nylon jersey and 1 g of cotton knit were wetted with hot water and drained, and then the Black HN dye used in Example 2 7.0% o. w. f. Asathiol Black SH (manufactured by Asahi Chemical Industry Co., Ltd.) 5.0% o. w. f. Add to 40 ml of dye bath. To this was added 0.3 ml of the acidic buffer solution at room temperature, and the temperature was raised, followed by staining at 85 ° C. for 30 minutes. Next, 3.2 g of sodium sulfate was added and staining was continued for 10 minutes. After 1.2 g of sodium carbonate and 1 g of redol C (manufactured by Sumitomo Chemical Co., Ltd.) as a reducing agent were added and stained for 40 minutes, Liquid, washed with water, neutralized with 48% acetic acid, sufficiently oxidized with hydrogen peroxide (3 g / l), washed with water, soaped and finished.

  As a result, both fibers were dyed to a thick black, and a dyed product having excellent same color was obtained. Washing, lightfastness, and various fastnesses such as chlorine were also cleared.

Example 6
Yoko: 10 g of 7 cm wide unwoven fabric composed of 6% nylon yarn 40% / warp: 60% cotton yarn, 30 g / l of Black HN dye used in Example 2, Mikethrene Direct Black S / F. (C.I.Vat Black 9) After immersing in a dye solution containing 60 g / l for 5 seconds, immediately squeezed uniformly with a two-roll mangle (squeezing rate 90%), both ends 7 cm wide and 5 cm long Tie with a polyester cloth, take up with a glass rod, and transfer to a small jigger dyeing machine (Jigger). After injecting 5 ml of the above acid side buffer and 50 ml of sodium sulfate 80 g / l into this jigger dyeing machine, the cover is covered and heated up to 90 ° C. to 100 ° C. While dyeing the dyed material from the tip, dipping and winding, dye it for 50 minutes while dipping alternately from the tip and end and winding up.

  Then, after cooling to 60 ° C. and adding 40 ° Be ′ caustic soda 30 ml / l, adding 15 g / l of hydrosulfite as a reducing agent and dyeing while winding for 15 minutes. Furthermore, 40 ° Be ′ caustic soda 5 ml / l and hydrosulfite 5 g / l are added, dyeing while winding for 10 minutes, and then draining. Next, water was sufficiently poured into the jigger and washed, and 48% acetic acid was added at 5 ml / l to neutralize, oxidized with hydrogen peroxide 2 ml / l, washed with water, and thoroughly soaped to finish.

As a result, both fibers were dyed in the same color and dark Grey color. As for the fastness of dyeing, particularly excellent results were obtained in washing, light fastness, sweat light fastness, and chlorine fastness, and the highest quality Grey color was obtained.

Claims (8)

6-Nylon jersey and un mercerized cotton knit in a 1: 1 weight ratio,
In a dyeing bath having a pH of 6.3 to 7.0 and a bath ratio of 1:20 to which 40 to 80 g / l of sodium sulfate is added, 5% o. w. f. , 10% o. w. f. For dyes other than Navy and Black dyes, 2% o. w. f. The density of 6-nylon jersey when dyed with NPA is NPA, and the density of unsilqueted cotton knit is NC,
Sodium sulfate 40-80 g / l and acetic acid 1% o. w. f. In a dye bath with a bath ratio of 1:20 and 2% o. w. f. When the density of 6-nylon jersey is APA and the density of unsilqueted cotton knit is AC,
NPA / NC is 200% or more, APA / AC is 200% or more, APA / NPA is 80 to 200%, and each correction color difference is 5.0 or less,
When the synthetic polyamide fiber is dyed, the dyed product is an alkali for 15 minutes at a bath ratio of 1:20 containing 40 ° Be ′ caustic soda 15 ml / l and hydrosulfite 5 g / l as a reducing agent at a temperature of 60 ° C. Withstand reducing conditions,
Using a water-soluble HN dye selected from acid dyes, acid metal-containing dyes, disperse dyes, and reactive dyes , one-bath system is used to dip a composite material containing synthetic polyamide fibers and cellulose fibers, and after the dip dyeing, alkali A method for dyeing a composite material, characterized by performing reduction. Alkaline reduction is performed using a reducing bath containing an alkaline agent having a pH of 9.0 to 12.5 at 20 ° C. and a reducing agent having a reduction potential (−mV) in the alkaline bath of 300 to 1200. The staining method according to claim 1 , wherein The method for dyeing a composite material according to claim 1 or 2 , wherein the dip dyeing is performed by mixing an alkali reducing dye together with an HN dye. The dyeing method according to claim 3 , wherein the alkali-reducing dye is selected from vat dyes, sulfur dyes and indigo dyes. The dyeing method according to claim 3 or 4 , wherein the hue of the alkali-reducing dye is different from the hue of the HN dye, and the synthetic polyamide fiber and other fibers are dyed in different colors. 6. The method for dyeing a composite material according to claim 3, wherein camouflage color dyeing is obtained. 3. The method for dyeing a composite material according to claim 1 or 2 , wherein the dyeing is white-remaining dyeing. A composite material containing a synthetic polyamide fiber, characterized by being dyed by the dyeing method according to any one of claims 1 to 7 .