JPH0745632B2 - Monoazo compound and dyeing method for hydrophobic fiber using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a monoazo compound and a method for dyeing a hydrophobic fiber characterized by using the same.

Conventional technology Recently, in the clothing industry, there is a strong tendency toward differentiation of textile products, and there is a path toward higher quality and higher added value. For this purpose, various processing methods are used even in the preparation of dyed cloth. Has been put to practical use. For example, antistatic processing of dyed cloth, texture finishing processing, and the like.

On the other hand, as for the dyeing method of textile products, not only plain dyeing by the dyeing method and pad dyeing method, which are the most popular dyeing methods for the purpose of increasing the added value of dyed goods, but also a printing method that can obtain a complicated pattern, Dyeing by the discharge method is increasing. Among them, in the dyeing by the discharge prevention method, it is necessary to use a dye having a structure in which the dye is easily decomposed into a colorless substance by the discharge preventing agent or the dye does not show dyeing property to the fiber. Furthermore, in this preventive discharge printing method, a dye which is not affected by the preventive discharge printing agent is used in combination to dye the discharged discharge portion in a hue different from the already dyed color (ground color) (colored preventive discharge printing method). Has also been done. In such a case, in addition to the usual dyeing characteristics, it is necessary to use a so-called color-dyeing dye having sufficient resistance to the anti-discharge printing agent used.

Thus, there is a demand for dyes that have excellent fastness after various post-treatments and that are compatible with a wide variety of dyeing methods. There are few quality products. In particular, there are few dyes that are sufficiently resistant to the alkaline discharge printing agent in the above-described colored discharge printing method.

As the color-imparting dye in the alkaline discharge printing method, which has been increasingly adopted recently, few azo dyes are satisfactory, and anthraquinone dyes have been mainly used. However, anthraquinone dyes generally have inferior color value compared to azo dyes, and because they are dyed in an alkaline medium that is different from usual dyes, their dyeing properties deteriorate, and the discharge area is dyed in a dark color. Has the disadvantage that it requires the use of a considerable amount of dye. Also, anthraquinone dyes are not suitable for reduction discharge printing.

Problems to be Solved by the Invention There is a demand for development of an azo red disperse dye which is excellent in alkali resistance, reduction discharge property and dyeing buildup property.

Means for Solving the Problems As a result of diligent efforts to solve the problems as described above, the inventors of the present invention have formula (I). [In the formula (I), X ₁ , X ₂ , X ₃ and X ₄ are each independently a hydrogen atom, a chlorine atom or a bromine atom, and Y is a hydrogen atom, a chlorine atom,
Or a C ₁ -C ₂ alkyl group, R is a C ₁ -C ₆ optionally branched alkyl group, an allyl group or (N is 1 or 2) and Z is Represents

However, at least two of X ₁ , X ₂ , X ₃ , and X ₄ are hydrogen, but none of them is a hydrogen atom. The present invention has been completed by finding that the monoazo compound represented by the following formula is excellent in alkali resistance, reduction discharge discharge property, dyeing property and build-up property.

The monoazo compound represented by the formula (I) has the formula (II) [In the formula (II), X ₁ , X ₂ , X ₃ and X ₄ each independently represent a hydrogen atom, a chlorine atom or a bromine atom. However, at least two of X ₁ , X ₂ , X ₃ , and X ₄ are hydrogen, but none of them is a hydrogen atom. ] The 2-aminobenzothiazole derivative represented by the formula (III) is diazotized by a known method in a mineral acid or a mixture of a mineral acid and an organic acid. [In the formula (III), Y is a hydrogen atom, a chlorine atom, or C _{1 to} C ₂
R is an alkyl group or an allyl group which may be branched from C _{1 to} C ₆ , or (N is 1 or 2) and Z is Which is represented by the formula

Specific examples of the diazo component represented by the formula (II) include the followings.

Specific examples of the coupler represented by the formula (III) include the following. To apply the monoazo compound of the present invention to a hydrophobic fiber, a suitable dispersant for the monoazo compound represented by the formula (I), for example, a formalin condensate of naphthalenesulfonic acid or an anionic dispersant such as ligninsulfonic acid, or ethylene oxide is used. A fine particle dye which is obtained by adding a nonionic activator such as a block copolymer with propylene oxide or an ethylene oxide adduct of alkylphenol and a small amount of water and thoroughly wet pulverizing it with a ball mill or a sand mill and then drying it in a paste form. To be used as.

Examples of the hydrophobic fiber that can be dyed with the monoazo compound of the present invention include polyester fiber, polyamide fiber, cellulose diacetate fiber, and cellulose oriacetate fiber. The best results are obtained when applied to polyester fiber.

The method for dyeing the monoazo compound of the present invention onto hydrophobic fibers, particularly polyester fibers, is a method known per se, for example, high temperature and high pressure (HT) dyeing method, carrier (Ca) dyeing method, pad dyeing method, textile printing method, A thermosol dyeing method or the like is used.

Further, in order to carry out reduction prevention discharge printing using the monoazo compound of the present invention, for example, intermediate drying is carried out by applying the monoazo compound of the present invention onto a cloth dyed with the above-mentioned method or by applying it by a pad method or a printing method. It is carried out by printing a reduction-preventing discharge-removing agent and a reduction-preventing discharge-removing paste containing a reduction-preventing discharge auxiliary on a cloth, and then performing high-temperature high-pressure steaming or high-temperature steaming.

Further, in order to use the monoazo compound of the present invention as a color-imparting dye in alkaline discharge printing, for example, the following method is carried out.

That is, on a fabric which has been dyed with an alkali-proof dischargeable dye by a dipping method or a printing method in advance, or on a cloth which has been subjected to an intermediate drying by applying the alkali-proof dischargeable dye by a pad method or a printing method. After printing a printing paste consisting of the monoazo compound of the invention, an alkaline discharge printing agent, and other auxiliary agents,
Perform high temperature high pressure steaming or high temperature steaming. A colored discharge cloth (dyed cloth) in which the discharge area is dyed red is obtained.

As the paste constituting the reduction-preventing discharge paste or the alkali-preventing discharge paste, starches, natural or synthetic starches, seaweeds, fibrin derivatives, etc. are used alone or in combination of two or more. As a method of applying the above, other than the usual simple mixing method, it is used as a W / O type or O / W type emulsion.

Examples of the reducing agent for preparing the reduction preventive discharge paste include zinc dust, acidic sodium sulfite, stannous chloride, processed stannous chloride, tin acetate, dechlorin, and Rongalit. Further, saccharides (eg, glucose, mannose, galactose, ribonose, xylose, arabinose, lactose, maltose, dextrin, glucan, glycogen, etc.) that stably function as a reducing agent even in the presence of an alkaline agent and an alkaline agent, saccharide derivatives (eg L- Ascorbic acid, isoascorbic acid, etc.), tannic acid, thiourea dioxide, organic mercapto compounds or organic sulfur compounds that form organic mercapto compounds when heated (for example, ethylmethylcaptan, 2-mercaptoethanesulfonic acid, 2-mercaptoacetic acid, Thiophenol, dithioglycolic acid, or alkali salts thereof) may also be used alone or in combination. Examples of the alkaline agent for preparing the Arali prevention discharge paste include bases having a pH value of 8 or more in a 5% aqueous solution, that is, hydroxides of alkali and alkaline earth metals (eg sodium hydroxide, potassium hydroxide), alkali metals. And alkaline salts of weak inorganic acids (eg, alkali metal carbonates, bicarbonates, phosphates, silicates), salts of alkali metals and organic acids (eg, alkali metal formates), ammonia or aliphatic amines (For example, triethylamine and its derivatives, ethanolamine and its derivatives, diethanolamine and its derivatives, triethanolamine) and the like can be mentioned, and these can be used alone or in combination of two or more kinds.

In the various dyeing methods described above, the use of a mixture of the compound of the present invention with another dye does not impair the characteristics of the compound of the present invention. As is well known, in certain combinations with mixed dyes, the dyeing density is higher than when used alone.

EXAMPLES The present invention will be described in more detail by way of examples. In the examples, parts and% mean parts by weight and% by weight.

Example 1. 1: 1 mixture of 2-amino-5,6-dichlorobenzothiazole and 2-amino-6,7-dichlorobenzothiazole 21.9
Parts was dissolved in 184 parts of concentrated sulfuric acid, and 124 parts of water was added dropwise at 40 ° C or lower. This was cooled to −4 ° C., 39 parts of 43% nitrosyl sulfuric acid was added dropwise over 1 hour, and then the mixture was stirred at −3 to 0 ° C. for 2 hours. The diazo solution thus obtained was added to 220 parts of 10% sulfuric acid and N-ethyl-N.
To the solution prepared by dissolving 24.4 parts of-(2- (2-pyridyl)) ethylaniline was added dropwise at 5 ° C or lower while appropriately adding ice water,
The mixture was stirred at the same temperature for 2 hours.

Then, the pH of the reaction solution is adjusted to 3 to 4 with 28% caustic soda.
Then, the temperature was raised to 40 ° C. and the mixture was stirred at the same temperature for 30 minutes, the product was separated, washed with water and dried to obtain 54.4 parts of a 1: 1 mixture of the compounds of the following formulas (IV) and (V). The λmax (in acetone) of the mixture was 535 nm.

Examples 2 to 16. The following compounds were obtained by changing the diazo component and the coupling component in the same manner as in Example 1.

Example 17. (Dyeing method of polyester fiber) (A) Preparation of finely divided dye 15 parts of monoazo compound obtained in Example 1, 20 parts of demall N (dispersing agent manufactured by Kao Atlas Co., Ltd.), 15 parts of demole C (at least Kao Atlas) (Manufactured by the company, dispersant)
And 80 parts of water were mixed, and the mixture was atomized using a sound grinder to a maximum diameter of 5 μm or less, and dried to obtain a dye powder.

(B) Dyeing 0.1 part of the finely-divided dye obtained above is dispersed in 150 parts of water, the pH is adjusted to 4.5 with acetic acid and sodium acetate, 5 parts of polyester fiber cloth is added, and the mixture is heated at 130 ° C. under pressure of 60 parts.
After dyeing, take out and wash with water.

Next, using 3000 parts of a solution prepared by dissolving 2 parts of caustic soda, 2 parts of hydrosulfite, and 1 part of Sunmor RC700 (reducing cleaning aid manufactured by Nichika Chemical Co., Ltd.) in 1000 parts of water, reduction is carried out at 80 ° C. for 10 minutes. It was washed, washed with water and dried. A red dyed fabric is obtained.

(C) Post-processing Treatment The dyed cloth obtained in (B) was dipped in a liquid prepared by dissolving 1 part of Nice Ball FL (an antistatic agent manufactured by Nichika Chemical Co., Ltd.) in 100 parts of water,
After squeezing evenly, perform intermediate drying at 100 ℃ for 3 minutes, and further 150
Antistatic processing was performed by curing at 3 ° C. for 3 minutes. There was no discoloration before and after processing, and no deterioration in water, washing fastness, etc. was observed.

Example 18. (Dip dyeing method) The monoazo compound obtained in Example 7 was treated in the same manner as in Example 17 with a finely divided dye.
A polyester fiber was dyed in the same manner as in 17 to obtain a red dyed product.

(A) Preparation of printing dye paste 3 parts of the micronized dye prepared in Example 17 (A), 60 parts of the base paste having the following composition and 37 parts of water are mixed well.

(Original paste composition) (B) Printing The polyester fiber cloth was printed with the printing dye paste prepared in (A) above, subjected to high-temperature steam heat treatment at 170 ° C. for 8 minutes, washed with water and reduced, then washed with water and dried. A red dyed product was obtained which was excellent in post-processing fastness.

Example 20 (Reduction discharge printing method of polyester fiber) (A) Preparation of reduction discharge paste A reduction discharge paste having the following composition was prepared.

(B) Reduction discharge dyeing The dyeing cloth obtained in (B) of Example 19 was printed with the reduction discharge paste prepared in (A) above, subjected to high-temperature steam heat treatment at 180 ° C. for 8 minutes, and washed with water and reduction. Then, it was washed with water and dried. The obtained dyed cloth was white in the part printed with reduction discharge paste, and the whiteness of the discharge part was excellent.
There was no discoloration or blurring at the boundary.

Example 21. (Application as a color dye for alkaline discharge) (A) Preparation of dye 30 parts of the compound obtained in Example 1, 35 parts of demol N, 35 parts of demol C and 100 parts of water were mixed and a sand grinder was used. It was used to make fine particles until the maximum particle diameter was 5 μm or less, and dried to obtain a dye powder.

(B) Preparation of printing paste A printing paste having the following composition was prepared.

* 1 Disperse dye manufactured by Nippon Kayaku Co., Ltd. that is easy to discharge with reduced alkali * 2 Original paste described in Example 8 (A) (C) Preparation of alkaline discharge discharge paste An alkaline discharge discharge paste having the following composition was prepared.

(D) Alkali-preventive discharge printing A polyester fiber cloth was printed with the printing dye paste prepared in (B), and was intermediate-dried at 100 ° C. for 3 minutes.

Next, the alkaline discharge-proofing paste prepared in (C) was printed in a constant width in an oblique direction and dried at 100 ° C. for 3 minutes. This dry cloth is subjected to high temperature steam heat treatment at 170 ° C for 8 minutes, then washed with water,
Washing with hot water, reduction washing, washing with hot water, and washing with water were performed in this order and dried.
The obtained dyed cloth had a striped pattern in which a yellow background color and a red line having a constant width were obliquely entered.

No discoloration or discoloration of the red part of the "pattern" due to the alkali removal paste was observed.

Example 22. (Composite discharge prevention method) (A) Preparation of pad solution A pad solution having the following composition was prepared.

(B) Preparation of Alkali Preventing Paste It was prepared in the same manner as in Example 21 (C).

(C) Preparation of reduction-preventing paste A reduction-preventing paste having the following composition was prepared.

(D) Preventive discharge treatment A polyester fiber cloth was dipped in the pad solution of (A) above, uniformly squeezed, and then dried at 100 ° C. for 3 minutes to obtain a dried cloth.

The dried cloth was imprinted with (B) the alkaline discharge printing paste through a screen on a "leaf" pattern, and was intermediately dried. Subsequently, (C) the reduction-preventing paste was applied to a "flower" pattern through a screen to perform intermediate drying, followed by high-temperature steam heat treatment at 175 ° C for 8 minutes, washing with water, reducing washing, washing with water, and drying.

A cloth was obtained in which a red "leaf" pattern and a yellow "flower" pattern were dyed on a black background. The "leaf" pattern at the intersection of the "leaf" pattern and the "flower" pattern disappears and becomes a "flower" pattern.
The pattern of the pattern was clear, and the compound of the present invention (monoazo compound of Example 2) had excellent alkali resistance. Therefore, the red color of the "leaf" pattern was clear and no decrease in density was observed.

Effect of the Invention A red, monoazo compound having excellent alkali resistance, dyeing property and build-up property is obtained, which is used for dyeing hydrophobic fibers such as polyester fibers and blended fibers thereof with cotton fibers and the like. It

Claims (2)

[Claims] 1. A formula [In the formula (I), X ₁ , X ₂ , X ₃ and X ₄ are each independently a hydrogen atom, a chlorine atom or a bromine atom, and Y is a hydrogen atom, a chlorine atom,
Or a C ₁ -C ₂ alkyl group, R is a C ₁ -C ₆ optionally branched alkyl group, an allyl group or (N is 1 or 2) and Z is Represents However, at least two of X ₁ , X ₂ , X ₃ , and X ₄ are hydrogen, but none of them is a hydrogen atom. ] A monoazo compound represented by 2. A formula [In the formula (I), X ₁ , X ₂ , X ₃ and X ₄ are each independently a hydrogen atom, a chlorine atom or a bromine atom, and Y is a hydrogen atom, a chlorine atom,
Or a C ₁ -C ₂ alkyl group, R is a C ₁ -C ₆ optionally branched alkyl group, an allyl group or (N is 1 or 2) and Z is Represents However, at least two of X ₁ , X ₂ , X ₃ , and X ₄ are hydrogen, but none of them is a hydrogen atom. ] The dyeing method of the hydrophobic fiber characterized by using the monoazo compound shown by