JPS6212829B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to anthraquinone compounds and anthraquinone dyes for cellulose-containing fibers. Specifically, the present invention relates to a reactive anthraquinone dye that dyes cellulose-containing fibers, particularly cellulose fibers, and mixed fibers consisting of polyester fibers and cellulose fibers in a fast and bright manner. The present invention will be explained in detail below. The present invention is based on the following general formula [] [In the formula, X is an amino group, a mono- or di-alkylamino group having a total of 1 to 6 carbon atoms, an anilino group,
Lower alkoxy group or -O( ^-R3O ) _-nR4 group (however, ^R3 is ^an ethylene group or a propylene group, ^R4
represents a methyl group or an ethyl group, m is 1 to 5
is an integer. ), and R ¹ and R ² represent an amino group or a hydroxyl group. ] This article focuses on anthraquinone compounds shown in the following and anthraquinone dyes for cellulose-containing fibers. . The anthraquinone compound represented by the above general formula [] is, for example, the following general formula [] (In the formula, R ¹ and R ² are the same as defined above.) The compound represented by the following general formula [] (In the formula, X is the same as defined above.) It can be produced by cyanurizing with a compound represented by the following. In the general formulas [] and [], the mono- or di-alkylamino group having 1 to 6 carbon atoms in total is a methylamino group, an ethylamino group, a linear or branched propylamino group. group, butylamino group, pentylamino group, hexylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, and the like. Examples of the lower alkoxy group include a methoxy group, an ethoxy group, a linear or branched propoxy group, and a butoxy group. Further, in the general formula [], m is an integer of 1 to 5, and 1 to 3 is particularly preferable. R ¹ and R ² represent a hydroxyl group or an amino group, but it is preferable that they are different from each other. Cellulose-containing fibers that can be dyed with the dye of the present invention include natural fibers such as cotton and hemp, semi-synthetic fibers such as viscose rayon and copper ammonia rayon, and partially aminated or partially acylated modified cellulose fibers. Examples include fibers, woven and knitted fabrics, and nonwoven fabrics thereof. In addition, the above fibers, polyester fibers, cationically dyeable polyester fibers, anionically dyeable polyester fibers, polyamide fibers, wool, acrylic fibers, urethane fibers,
Examples include blended or woven products with other types of fibers such as diacetate fibers and triacetate fibers. Among these, the dye of the present invention is particularly effective for cellulose fibers and blended or woven products of cellulose fibers and polyester fibers. As a method for dyeing the cellulose-containing fibers with the dye of the present invention, Padein 9 dyeing method or textile printing method is suitable, but dyeing can also be carried out by wet or dry transfer printing method. Conventionally, in padding dyeing and printing dyeing of cellulose fibers, dyes such as direct dyes, sulfur dyes, patch dyes, naphthol dyes, and water-soluble reactive dyes have been used. However, since none of the former four dyes are dyed with cellulose fibers through covalent bonds, they have problems in wet fastness and rubbing fastness. For these reasons, water-soluble reactive dyes are widely used, but it is known that these water-soluble reactive dyes also have the following problems. 1. Dye utilization rate is low at around 50-70%. 2. In order to obtain good wet fastness, which is a characteristic of water-soluble reactive dyes, it is necessary to completely remove unreacted dyes from the fibers, which requires a large amount of water in the washing process. Naturally, treatment of colored wastewater is also required in conjunction with this. On the other hand, in padding dyeing and printing dyeing of a mixed material consisting of polyester fibers and cellulose fibers having completely different degrees of hydrophilicity, the polyester fiber side is dyed with a disperse dye and the cellulose fiber side is dyed with the various dyes exemplified above. Generally, a combination of a disperse dye and a water-soluble reactive dye is widely used from the viewpoint of wet fastness and rub fastness of dyed products. Furthermore, as dyeing methods, the one-bath one-stage padding dyeing method and the one-phase printing method are attracting the most attention from the viewpoint of economic efficiency. However, it is known that this case has the following problems. 1. Approximately 2% by weight of alkali, such as sodium carbonate, is usually added to the padding bath or printing dye paste as a reaction catalyst for water-soluble reactive dyes, but this decomposes the disperse dyes during heat fixation and reduces the dye density. It can cause yellowing of cellulose and make the hue unclear. 2. The utilization rate of the water-soluble reactive dye is much lower than that of dyeing cellulose fiber alone because the dye attached to the polyester fiber is not utilized.
Therefore, it is necessary to use an excess of water-soluble reactive dye. 3 It goes without saying that a large amount of washing water is required to completely remove unreacted water-soluble reactive dyes and unfixed disperse dyes from fibers, which are factors that reduce the light fastness and wet fastness of dyed products. However, at this time, the unfixed disperse dye removed from the fibers also contaminates the cellulose fiber side or the area that is to be left as a white area. On the other hand, methods of dyeing these mixed materials with a single dye are also known. One known method is the so-called pigment resin method, in which pigments are attached to fibers using resin, but this method has problems with the texture and abrasion fastness of the dyed product. Furthermore, a method using a specific nonionic dye having a slightly larger molecular weight than ordinary disperse dyes for polyester fibers is known. Since this dye is adsorbed onto cellulose fibers, it will bleed if left for a long time. Furthermore, because the molecular weight is larger than that of ordinary disperse dyes, the temperature dependence during fixation is large and the reproducibility is low. These problems can be solved by using the dye represented by the above general formula []. The staining method will be explained in more detail below. When carrying out dyeing, please follow the general formula shown above []
It is desirable to finely disperse the dye represented by 0.5 to 2 μ in a medium using a nonionic or anionic dispersant such as sodium lignosulfonate or sodium salt of naphthalenesulfonic acid-formalin condensate. A method that uses a water-soluble dispersant and finely disperses it in water using a grinder such as a sand grinder or a mill, or a method that uses a water-soluble dispersant such as a sand grinder or a mill to finely disperse it in water. Using a dispersant, solvents other than water, such as alcohols such as ethyl alcohol, isopropyl alcohol, and polyethylene glycol, ketones such as acetone and methyl ethyl ketone, hydrocarbons such as n-hexane, toluene, xylene, and mineral turpentine, and tetrachloroethylene, etc. A method of finely dispersing halogenated hydrocarbons, esters such as ethyl acetate and butyl acetate, ethers such as dioxane and tetraethylene glycol dimethyl ether, or a mixed solvent thereof, water and any of the above solvents. Examples include a method of finely dispersing the compound in a mixed system with a solvent that can be mixed with the compound. Furthermore, in the above-mentioned fine dispersion process, a polymer compound soluble in each dispersion medium or a surfactant having a function other than the dispersion effect may be added. This dye fine dispersion can be used as it is as a padding bath in padding dyeing method and as printing dyeing paste in textile printing method, but when used as a normal padding bath and printing dyeing paste, the above dye fine dispersion can be mixed with water or optionally with water. A mixed system of solvent and water that can be mixed with water or an O/W emulsion system in which the oil layer is a petroleum hydrocarbon such as mineral turpentine or a halogenated hydrocarbon such as tetrachloroethylene is diluted to a ratio according to the desired dyeing density. is used. In order to advantageously carry out the present invention in preparing the padding bath and printing dyeing paste, an acid binder such as an alkali metal carbonate may be added for the purpose of promoting the reaction between cellulose fiber swelling agent or dye and cellulose fiber. . In addition, a thickener such as a water-soluble polymer such as sodium alginate may be added to prevent dry migration during padding dyeing or to adjust the viscosity of the color paste to be optimal for various printing methods. The preparation of the padding bath or printing dyeing paste is not limited to the above method, and the cellulose swelling agent and acid binder do not necessarily need to be present in the padding bath or printing dyeing paste, but are applied to the fiber side in advance. It may be left to exist. Any cellulose fiber swelling agent can be used as long as it has a boiling point of 150°C or higher and has the effect of swelling cellulose fibers. For example, N.N.
Examples include ureas such as N'·N'-tetramethylurea, polyhydric alcohols such as polyethylene glycol, polypropylene glycol, and derivatives thereof. Particularly preferred as the cellulose fiber swelling agent are polyhydric alcohol derivatives having an average molecular weight of about 200 to 500, such as polyethylene glycol and polypropylene glycol, in which the hydroxyl groups at both ends are dimethylated or diacetylated and do not react with the reactive groups of the dye. The appropriate amount of the cellulose fiber swelling agent to be used is about 5 to 25% by weight, preferably about 8 to 15% by weight, based on the padding bath or textile dyeing paste. In addition to alkali metal carbonates, acid binders include alkali metal fatty acids such as alkali metal bicarbonates, alkali metal phosphates, alkali metal borates, alkali metal silicates, alkali metal hydroxides, and alkali metal acetates. Salts or alkali precursor compounds that generate alkali when heated in the presence of water, such as sodium trichloroacetate and sodium acetoacetate, can be used. In addition, since the reactive monofluorotriazinyl group contained in the dye of the present invention is much more reactive than the monochlorotriazinyl group, the amount of acid binder used can be significantly reduced, and it can be used during dyeing. It can prevent the decomposition of dyes and yellowing of fibers. The amount of acid binder used is 0 to 0.1% by weight of the padding bath or textile dyeing paste in the case of monofluoroalkoxytriazinyl groups, and 0.1 to 0.2% by weight in the case of monofluoroaminotriazinyl groups. It is. In order to dye the fibers with the dye of the present invention, a padding bath or printing paste prepared by the above method is impregnated or printed on a material containing cellulose fibers, and after drying, a dyeing temperature of 160° to 220° is applied.
Heat treatment with hot air or superheated steam at ℃ for 30 seconds to 10 minutes,
Or in high pressure saturated steam at 120° to 150°C.
Treat for ~30 minutes and wash with hot water containing a surfactant, or O/W type or W/O where the oil layer is a halogenated hydrocarbon such as tetrachloroethylene.
This is completed by cleaning with a mold emulsion cleaning bath or with a conventional dry cleaning method. By the above method, it is possible to obtain a dyed product which is vividly and uniformly dyed and has good light fastness and wet fastness. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. In addition, "parts" in the examples indicate "parts by weight." Example 1 The following structural formula A dye dispersion was prepared from a dye composition consisting of 15 parts of anthraquinone dye represented by the formula, 15 parts of a naphthalene sulfonic acid-formaldehyde condensate, and 70 parts of water using a paint shaker as a fine dispersion machine. Using this dye dispersion, prepare a printing paste with the following composition: Dye dispersion 6.5 parts 5% sodium alginate aqueous solution 55 parts Polyethylene glycol dimethyl ether having an average molecular weight of 400 9 parts Water 29.45 parts Sodium carbonate 0.05 parts 100 g of printing paste for polyester/cotton (Mixing ratio 65/35) The blended fabric was printed using a screen printing machine, and after intermediate drying at 80℃ for 3 minutes, it was heated to 90℃ at 215℃.
Dry for seconds and heat set. After washing it with water, add 1 g of sodium hydroxide and 2 g of nonionic surfactant (Score Roll #900 (trademark), manufactured by Kao Soap Co., Ltd.).
20 at a bath ratio of 1:30 using a cleaning solution containing g/20
After soaping for a minute, a bright blue dyeing with excellent light fastness was obtained. A portion of the above dyed material is treated with 70% sulfuric acid to dissolve the cotton, the resulting polyester fibers and another portion are treated with hexafluoroisopropanol to dissolve the polyester, and the hue of the resulting cellulose fibers is obtained. When compared, it was found that the same hue was very good, and the light fastness of the dyed products of each fiber was also good. The dye used in this example was 1-(m-amino-
(phenylamino)-4,8-dihydroxy-5-
aminoanthraquinone in N-methyl-2-pyrrolidone using triethylamine as a deoxidizer;
It was obtained by reacting with 2,4-difluoro-6-methoxy-S-triazine. The λmax (acetone) of this product was 641 nm. Example 2 Structural formula below A dye dispersion was prepared from a dye composition consisting of 15 parts of an anthraquinone material, 15 parts of a naphthalene sulfonic acid-formaldehyde condensate, and 70 parts of water using a sand grinder as a fine disperser. Using this dye dispersion, a 100 g textile dyeing paste was prepared using the following composition: Dye dispersion 7 parts 5% sodium alginate aqueous solution 55 parts Polypropylene glycol diacetate with an average molecular weight of 300 12 parts Sodium carbonate 0.05 parts Water 25.95 parts , printed on mercerized broad cotton (number 40) using a screen printing machine, dried at 80℃ for 3 minutes, and then dried at 185℃ for 7 minutes.
Treatment was carried out using superheated steam for 1 minute. Thereafter, washing treatment was carried out according to the method described in Example 1, and a blue dyed product with excellent light fastness and wet fastness was obtained. The dye used in this example was 1-(m-aminophenylamino)-4,8-dihydroxy-5-aminoanthraquinone in N-methyl-2-pyrrolidone using triethylamine as a deoxidizing agent.
It was obtained by reacting with 2,4-difluoro-6-ethoxyethoxyethoxyethoxy-S-triazine. The λmax (acetone) of this product was 641 nm. Example 3 Structural formula below A dye composition consisting of 10 parts of anthraquinone dye shown in the formula, 2 parts of polyoxyethylene glycol nonyl phenyl ether (HLB8.9) and 88 parts of diethylene glycol diacetate was ground using a paint conditioner as a fine dispersion machine. A dye ink was prepared. After mixing 10 parts of this dye ink and 55 parts of mineral turpentine, this was stirred with a homomixer (5000~
7000 RPM), gradually pour into 35 parts of an aqueous solution with the following composition and stir until homogeneous.
A W-type emulsion colored paste was prepared. Water 31 parts Lepitol G (trademark, Daiichi Koyaku Yakuhin Co., Ltd., special nonionic surfactant) 3.8 parts Sodium trichloroacetate 0.2 parts 35 parts Next, use this color paste to make a polyester/cotton (mixing ratio 65/35) blended fabric. was printed using a screen printing machine, dried at 100°C for 2 minutes, and then treated with superheated steam at 175°C for 7 minutes. Thereafter, the dyed product was washed in a hot tetrachloroethylene bath containing a small amount of water and dried to obtain a bright blue dyed product with excellent wet fastness and no spot staining. The dye used in this example was 2.
It was obtained by reacting with 4-difluoro-6-diethylamino-S-triazine. The λmax (acetone) of this product was 641 nm. Example 4 Structural formula below A dye dispersion liquid was prepared by finely dispersing a dye composition consisting of 16 parts of the dye represented by, 10 parts of polyoxyethylene glycol nonyl phenyl ether (HLB13.3), and 74 parts of water using a sand grinder.
Using this dye dispersion, prepare a padding bath with the following composition: dye dispersion: 6 parts, tetraethylene glycol dimethyl ether, 15 parts, water, 78.8 parts, sodium trichloroacetate, 0.2 parts, 100 g, and apply it to a polyester/rayon (mixing ratio of 65/35) blended fabric. Impregnation and squeezing rate 75%
After squeezing, it was dried at 100°C for 2 minutes and fixed by dry heat at 200°C for 1 minute. By washing this product in a hot ethanol bath, a blue dyed product was obtained which was clear, free from irritation, and had excellent wet fastness. The dye used in this example was produced according to the method described in Example 1. The λmax (acetone) of this product was 641 nm. Example 5 Printing was carried out in the same manner as in Example 1 except that the fiber was changed to a nylon/rayon (mixing ratio 50/50) blended fabric and the drying fixation temperature was changed to 185°C. A print with good fastness and wet fastness and a clear blue color was obtained. According to microscopic observation, the printed material was uniformly dyed. Example 6 Mercerized broad cotton (number 40) was immersed in a treatment bath consisting of 0.14 parts of sodium carbonate, 25 parts of tetraethylene glycol dimethyl ether, and 75 parts of water, and after squeezing to a squeezing rate of 70%, it was heated at 50°C for 50 minutes.
Dry for a minute. On the other hand, 6 parts of the dye used in Example 1, 8 parts of ethyl cellulose, and 86 parts of isopropyl alcohol were ground with a paint conditioner to prepare an ink, and this ink was gravure printed on gravure coated paper to create a transfer sheet. did. The above-mentioned cotton cloth is superimposed on this transfer sheet, and the vacuum transfer machine Arilotsupah FV2-1019 (Naomoto Kogyo Co., Ltd.)
60 at 10Torr, 210℃, 100g/ ^cm2G
When the transfer was fixed by applying heat and pressure for a second, a clear blue dyed product was obtained. When the dyed product was washed with hot dimethylformamide, almost no dye was observed to come off. Example 7 Using the dyes shown in Table 1 below, if the reactive group is a monofluoroalkoxytriazinyl group, add 0.05% by weight of sodium carbonate as an acid absorbent (for printing paste), and if the reactive group is a monofluoroamino In the case of triazinyl groups, printing was carried out according to the method described in Example 1 using 0.2% by weight of sodium carbonate (for printing paste). As a result, prints with good wet fastness and light fastness of hues shown in Table 1 were obtained.

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Claims (1)

[Claims] 1. General formula [In the formula, X is an amino group, a mono- or di-alkylamino group having a total of 1 to 6 carbon atoms, an anilino group,
lower alkoxy group or -O( ^-R3O ) _-nR4 group (wherein ^R3 is ^an ethylene group or a propylene group,
R ⁴ represents a methyl group or an ethyl group, m is 1
It is an integer of ~5. ), and R ¹ and R ² represent an amino group or a hydroxyl group. ]An anthraquinone compound represented by. 2 General formula [In the formula, X is an amino group, a mono- or di-alkylamino group having a total of 1 to 6 carbon atoms, an anilino group,
Lower alkoxy group or -O( ^-R3O ) _-nR4 group (wherein ^R3 is ^an ethylene group or a propylene group,
R ⁴ represents a methyl group or an ethyl group, m is 1
It is an integer of ~5. ), and R ¹ and R ² represent an amino group or a hydroxyl group. ] Anthraquinone dye for cellulose-containing fibers.