JPH04110B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a monoazo compound and a dyeing or printing method using the same. For more details, please refer to the expression () [In formula (), X ₁ , X ₂ , X ₃ , and X ₄ each independently represent a hydrogen atom, a chlorine atom, a bromine atom, or a nitro group,
Y is a hydrogen atom, a chlorine atom, or a _C1 - _C2 alkyl group, and R is a _C1 - _C8 optionally branched alkyl group, an allyl group, or

[Formula] represents a group, and n represents 1 or 2. However, X ₁ , X ₂ ,
At least two of X ₃ and X ₄ are hydrogen, but 4
Neither is a hydrogen atom, except when X ₂ is a nitro group. ] The present invention relates to a monoazo compound represented by the following and a method for dyeing or printing hydrophobic fibers using the monoazo compound. Recently, in the clothing industry, there has been a strong trend toward differentiation of textile products, and the trend is toward higher quality and higher added value, and for this purpose, various processing methods are being put into practice when preparing dyed fabrics. has been made into For example, antistatic processing of dyed cloth, texture finishing, etc. On the other hand, regarding dyeing methods for textile products, in addition to the most common dyeing methods such as dip dyeing and pad dyeing, which are the most common dyeing methods for the purpose of increasing the added value of dyed products, printing methods that can produce complex patterns, Dyeing using the discharge printing method is becoming more common. Among these, in dyeing by the anti-discharge dyeing method, it is necessary to use a dye that is easily decomposed into a colorless substance by the anti-discharge agent, or has a structure that does not show dyeability to fibers. Furthermore, in this anti-discharge printing method, the discharge-printed area is dyed in a hue different from the already dyed color (ground color) by using a dye that is not affected by the anti-discharge dye (coloring). Anti-discharge dyeing method) is also used. In such cases, it is necessary to use a dye that has so-called contrast color suitability and has sufficient resistance to the anti-discharge dye used in addition to the usual dyeing properties. There is a demand for dyes that have excellent fastness after various post-processing processes and can be used with a wide variety of dyeing methods, but the products currently in use on the market do not meet these demands. There are few that are of sufficient quality. In particular, there are almost no dyes that are sufficiently resistant to the alkaline anti-discharge agent used in the above-mentioned colored anti-discharge printing method. As a result of our earnest efforts to meet such market demands, we have found that the monoazo dye represented by the above formula () exhibits strong dyeing properties on hydrophobic fibers, especially polyester fibers, and also has excellent fastness properties after subsequent processing, especially The present inventors have discovered that this dye not only has excellent fastness to water and perspiration, but also has excellent reduction discharge printing properties and alkali resistance, making it excellent as a dye for alkali discharge printing and contrast color printing. There are no satisfactory azo dyes as color dyes in the alkaline anti-discharge printing method, which has recently become more popular, and anthraquinone dyes have been mainly used. However, anthraquinone dyes generally have inferior color values compared to azo dyes, and because they are dyed in an alkaline medium, which is different from normal dyes, their dyeability is reduced, and the dyeing process is difficult to achieve in the discharge printing area. has the disadvantage that it requires the use of a considerable amount of dye. When the monoazo compound according to the present invention is used as an accent color dye in such an alkaline colored anti-discharge printing method, a colored discharge-printed fabric in which the anti-discharge dyed area is very clear and dyed in deep red can be easily obtained, and it is generally used. Even when applied to the dyeing method, printing method, and discharge printing method, it shows good dyeing properties and provides excellent fastness. The monoazo compound represented by the formula () is represented by the formula () [In the formula (), X ₁ , X ₂ , X ₃ , and X ₄ have the same meanings as above] is diazotized by a known method to obtain the formula () [In formula (), Y, R, and n represent the same meanings as above] It can be obtained by coupling with an aniline derivative represented by the following. Specific examples of the diazo component represented by formula () include the following.

【formula】

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[Formula] Further, specific examples of the coupler represented by the formula () include the following. To apply the monoazo compound of the present invention to hydrophobic fibers, a dispersant suitable for the monoazo compound represented by formula (), such as an anionic dispersant such as a formalin condensate of naphthalene sulfonic acid or lignin sulfonic acid, or ethylene oxide and propylene. Add a nonionic activator such as a block copolymer with oxide, an ethylene oxide adduct of alkylphenol, and a small amount of water, thoroughly wet-mill using a ball mill or sand mill, and then make a paste and dry to form a finely divided dye. provided for use as a Hydrophobic fibers that can be dyed with the monoazo compound of the present invention include polyester fibers, polyamide fibers, cellulose diacetate fibers, cellulose triacetate fibers, etc., but the best results are obtained when applied to polyester fibers. Methods for dyeing hydrophobic fibers, particularly polyester fibers, with the monoazo compound of the present invention include methods known per se, such as high temperature and high pressure (HT) dyeing method, carrier (Ca) dyeing method, pad dyeing method,
Textile printing methods, thermosol dyeing methods, etc. are used. Further, in order to carry out reduction-proof discharge printing using the monoazo compound of the present invention, for example, the monoazo compound of the present invention may be applied on a fabric dyed by the method described above, or applied by a pad method or a printing method, and then subjected to intermediate drying. After printing a reduction-discharge-proof printing paste containing a reduction-discharge-proof dyeing agent and a discharge-proof dyeing auxiliary agent on the fabric which has been subjected to this process, high-temperature, high-pressure steaming or high-temperature steaming is performed. In this case, as the reduction and discharge printing agent, for example, zinc powder, acidic sodium sulfite, stannous chloride, tin acetate, Rongarit, dechlorin, etc. are used. Further, in order to use the monoazo compound of the present invention as an accent color dye in alkaline anti-discharge printing, the following method is carried out, for example. In other words, the present invention is applied onto a fabric that has been previously dyed with a dye that can be resistant to alkali discharge printing by dipping or printing, or onto a fabric that has been applied with a dye that is resistant to alkali discharge printing using a pad method or a printing method and then subjected to intermediate drying. After printing, a printing paste consisting of the monoazo compound of the invention, an alkaline anti-discharge agent, and other auxiliary agents is subjected to high-temperature, high-pressure steaming or high-temperature steaming. A colored discharge-printed cloth (dyed cloth) in which the discharge-printed part is dyed red is obtained. In this case, the alkaline discharge printing agents include alkali and alkaline earth metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, calcium hydroxide), salts of alkali metals and inorganic weak acids (e.g.,
Alkali metal carbonates, bicarbonates, phosphates,
silicates), salts of alkali metals and organic acids (e.g. alkali metal formates), ammonia or aliphatic amines (e.g. triethylamine and its derivatives), and these may be used alone or in combination of two or more. be able to. Next, the present invention will be specifically explained using examples.
In the examples, "parts" and "%" are parts by weight and % by weight, respectively. Example 1 2-amino-6-chlorobenzothiazole 18.5
After dissolving 184 parts of concentrated sulfuric acid, dissolve 124 parts of water at 40°C or below.
part was dripped. This was cooled to -4℃ and 39 parts of 43% nitrosyl sulfuric acid was added dropwise over 1 hour.
Stirred at ℃ for 2 hours. 10% of the diazo liquid obtained in this way
% sulfuric acid and 21 parts of N-ethyl-N-benzylaniline, while adding ice water as appropriate.
The mixture was added dropwise at a temperature below .degree. C. and stirred at the same temperature for 5 hours. Next, the reaction solution was heated to 70° C. and stirred at the same temperature for 2 hours, and then the product was separated, washed with water and dried to obtain 35.3 parts of a compound of the following formula (). λmax (75% acetone water) = 520nm Example 2 21.9 parts of a 1:1 mixture of 2-amino-5,6-dichlorobenzothiazole and 2-amino-6,7-dichlorobenzothiazole and N-ethyl-N-β
- From 22.5 parts of phenylethylaniline, a mixture of the following formula () () 1:1 was prepared in the same manner as in Example 1.
Got 40.5 copies. The mixture had a λmax (in 75% acetone) = 534 nm. Example 3 Water was added to 3 parts of the compound of formula () obtained in Example 1, 3 parts of sodium ligninsulfonate, and 4 parts of a formalin condensate of naphthalenesulfonic acid to form a slurry, which was thoroughly wet-milled in a ball mill and thoroughly wet-pulverized in a spray dryer. After drying, a finely divided dye was obtained. 3 parts of the micronized dye obtained above was added to 3,000 parts of water, and the pH was adjusted to 5 with acetic acid and sodium acetate. 100 parts of Tetoron cloth (polyester fiber) was immersed in this dye solution and dyed at 130° C. for 1 hour. After washing with water, reduction washing, and drying, a vivid red dyed cloth is obtained, which has excellent light resistance, sublimation, washing, water,
It had excellent sweat fastness. In particular, the fastness to water and perspiration after antistatic processing and texture finishing was extremely good. Examples 4 to 21 Compounds were synthesized in the same manner as in Examples 1 to 2, and finely divided dyes were obtained in the same manner as in Example 3 and used for dyeing Tetoron cloth. Both gave red-dyed cloth. Table 1 shows the structural formulas of the compounds and their λmax.

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[Table] Example 22 A colored paste having the composition shown below was prepared using a finely divided dye prepared from the compound obtained in Example 2 in the same manner as in Example 3. This color paste was printed on Tetron cloth, and after intermediate drying at 80℃ x 3 minutes, it was heated to 175℃.
High temperature steaming was performed for 5 minutes. After washing with hot water, aqueous reduction washing, and drying, a vivid red print was obtained. This dyed product was excellent in various fastnesses, and in particular, the fastness to water and perspiration after post-processing was extremely good. <Color paste> Γ Micronized dye...3 parts Γ Fine Gum MC-8 (manufactured by Daiichi Kogyo Seiyaku)
7.0% Sorbitose C-5 (manufactured by Skorten)
4.5% Citric acid 0.33% Improver 880 (manufactured by Yokohama Polymer)
Base paste consisting of 3.3% and water...60 parts Γ water...37 parts Total 100 parts Example 23 A reduced discharge printing paste having the following composition was prepared. Example 22
This reduced discharge printing paste was printed on the printed fabric obtained in step 1 using a screen with a polka dot pattern, and after intermediate drying at 80°C for 3 minutes, high temperature steaming was performed at 170°C for 5 minutes. Then, by washing with hot water, washing with water, and reducing washing and drying, a red dyed cloth (washed cloth) with a polka dot pattern with excellent whiteness was obtained. <Reduction discharge dyeing paste> Γ urea...5 parts Γ water 5 parts Γ Faingum A-2159B (manufactured by Daiichi Kogyo Seiyaku) 16
% and water...50 parts ΓPrintgen ST-105 (Matsui Shiki)...2 parts ΓPEG-300 (polyethylene glycol)...3 parts ΓUniston AM-300 (Hayashi Kagaku)...30 parts ΓTeryl carrier BEL (Meisei Chemical)...5 parts Total 100 partsExample 24 Using a micronized dye prepared in the same manner as in Example 3 from the mixture of monoazo compounds obtained in Example 13, color paste (A) of the following composition, ( B) was prepared. These colored pastes (A) and (B) were printed in parallel on a piece of Tetron cloth, and after intermediate drying at 80°C for 3 minutes, high temperature steaming was performed at 175°C for 5 minutes. After washing with hot water, washing with water and reduction washing, and drying, a bright red print was obtained. In this dyed product, the color paste (A) part and the color paste part (B) in which soda ash coexisted had exactly the same hue and various fastnesses, and there was almost no difference in density. That is, the monoazo compound of the present invention exhibited good dyeing properties without decomposition, discoloration, density reduction, etc. even in the presence of an alkaline agent under normal printing conditions. <Color paste (A)> Γ micronized dye...2 parts Γ fine gum D-2514 (Daiichi Kogyo Pharmaceutical) 20%
Base glue consisting of and water…55 parts Γ Color Fine AD (manufactured by Daiichi Kogyo Seiyaku)…10 parts Γ Water…33 parts Total 100 parts <Color paste (B)> Γ Micronized dye…2 parts Γ Fine Gum D- 2514 Base glue consisting of 20% and water...55 parts Γ soda ash...5 parts Γ Color Fine AD...10 parts Γ water...28 parts Total 100 partsExample 25 In Example 24, soda ash in colored paste (B) A similar printing test was carried out using potassium carbonate instead. As a result, as in Example 24, there was almost no difference in dyeability due to the presence of the alkaline agent (potassium carbonate). Example 26 A pad solution and alkaline resist dye paste were prepared with the following compositions. Tetron diose cloth was first dipped in this pad solution, squeezed to 80% with a mangle, and then intermediately dried at 80°C for 3 minutes. Next, this alkaline resist printing paste was printed on the fabric using a floral screen, and after intermediate drying was performed again at 80°C for 3 minutes, steaming was performed at 175°C for 5 minutes using heated steam. After washing with water, hot water, reduction washing, and drying, a colored discharge-printed cloth with a clear red floral pattern on a black background was obtained. <Paste liquid> ΓKayalon Polyester Black GD-S Paste
(Nippon Kayaku black disperse dye for alkaline discharge printing)
…200 parts ΓSnow Algin SSL (manufactured by Fuji Chemical)…1 part Γcitric acid…2 parts ΓSuccinol CS-K (manufactured by Nippon Someka)…0.5 parts Γwater…796.5 parts Total 1000 parts <Alkaline resist dye paste> Micronized dye obtained in Γ Example 24...Glue consisting of 2 parts Γ Fine Gum D-2514 20% and water
...55 parts Γ Soda ash ... 5 parts Γ Color Fine AD ... 10 parts Γ Water ... 28 parts Total 100 parts Example 27 An alkaline discharge printing paste was prepared with the following composition. Tetron dioset cloth was immersed in the padding solution used in Example 26, squeezed to 80% with a mangle, and after intermediate drying, high temperature steaming was performed at 175° C. for 5 minutes. Next, wash with water, hot water, reduction wash, dry,
A black printed cloth was obtained. This alkaline discharge paste was printed on the printed fabric using a floral screen, and after intermediate drying, high temperature steaming was performed at 175° C. for 5 minutes. After washing with hot water, water, reduction washing, and drying, a colored discharge-printed cloth with a clear red floral pattern on a black background was obtained. <Alkali discharge printing paste> Glue consisting of micronized dye obtained in Γ Example 24...2 parts Γ soda ash...5 parts Γ dicyandiamide...2 parts Γ Fine Gum D-2514 20% and water
…70 parts Γ Color Fine AD…10 parts Γ Day Paint PC (manufactured by NICCA Chemical)…5 parts Γ Water…6 parts Total 100 parts

Claims (1)

[Claims] 1 formula [In formula (), X ₁ , X ₂ , X ₃ , and X ₄ each independently represent a hydrogen atom, a chlorine atom, a bromine atom, or a nitro group.
represents a hydrogen atom, a chlorine atom, or a _C1 - _C2 alkyl group, R represents a _C1 - _C8 optionally branched alkyl group, an allyl group, or a [Formula] group, and n is 1 or 2. represents. However, X ₁ , X ₂ ,
At least two of X ₃ and X ₄ are hydrogen, but 4
Neither is a hydrogen atom, except when X ₂ is a nitro group. ] A monoazo compound represented by 2 formulas [In formula (), X ₁ , X ₂ , X ₃ , and X ₄ each independently represent a hydrogen atom, a chlorine atom, a bromine atom, or a nitro group.
represents a hydrogen atom, a chlorine atom, or a _C1 - _C2 alkyl group, R represents a _C1 - _C8 optionally branched alkyl group, an allyl group, or a [Formula] group, and n is 1 or 2. represents. However, X ₁ , X ₂ ,
At least two of X ₃ and X ₄ are hydrogen, but 4
Neither is a hydrogen atom, except when X ₂ is a nitro group. ] A method for dyeing or printing hydrophobic fibers, characterized by using a monoazo compound represented by the following.