KR0148440B1 - Method for manufacturing novel heterocycle disperse dyes compounds - Google Patents

Abstract

The present invention relates to novel heterocycle compounds of the general formula (I) below which are useful for dyeing or printing hydrophobic fibers, such as polyester fibers, and methods for their preparation. The present invention also relates to a method of dyeing or printing a fiber material using the compound of the general formula (I).

Wherein R ¹ represents a substituted or unsubstituted unsaturated aromatic group of the general formula

Wherein R ² represents C ₁ -C ₄ alkyl, R ³ represents C ₁ -C ₄ alkyl or alkoxy and X represents a halogen atom.

Description

Novel heterocycle disperse dye compound and preparation method thereof

The present invention relates to novel heterocycle compounds of the general formula (I) below which are useful for dyeing or printing hydrophobic fibers, such as polyester fibers, and methods for their preparation. The present invention also relates to a method of dyeing or printing a fiber material using the compound of the general formula (I).

In the above formula,

R ¹ represents a substituted or unsubstituted unsaturated aromatic group of the general formula

here,

R ² represents C ₁ -C ₄ alkyl,

R ³ represents C ₁ -C ₄ alkyl or alkoxy,

X represents a halogen atom.

Recently, as consumers' preference for high-quality clothing increases, the demand for disperse dyes having excellent effects on dyeability and various fastnesses to hydrophobic fibers is also increasing. In order to increase the added value of the product after dyeing or printing, the hydrophobic or hydrophobic fiber is often subjected to post-processing such as softening, antistatic, and tactile improvement. Such post-processing is usually performed at high temperature. Therefore, the bleed (bleed) problem of the dye is generated, so that the wet fastness of the dye or the printing material, and among them, in particular, the wash fastness occurs.

Conventionally, development of a disperse dye for obtaining dyeing or printing with excellent washing fastness has been mainly made for azo compounds, and therefore many azo compounds have been proposed. However, these known compounds are insufficient to solve the above problems, and still the washing fastnesses of the dyes or prints during the post-processing are significantly reduced.

On the other hand, Japanese Patent Application Nos. 52-1,095,206, 56-122,869 and 60-152,567 disclose benzodifuranone compounds useful for dyeing or printing hydrophobic fiber materials, but these benzodifuranone compounds are also dyeable. Insufficient to satisfy both the and the fastness at the same time, improvement is desired.

Accordingly, the present inventors have conducted extensive research over a long period of time to solve the conventional problems as described above, and as a result, the novel heterocycle compound of general formula (I) is used to dye or print a hydrophobic fiber material such as polyester. In addition to exhibiting excellent dye properties, the present invention has been found to be excellent in wet fastness, sublimation fastness, light fastness and the like.

Hereinafter, the configuration of the present invention will be described in detail.

The present invention relates to novel heterocycle compounds of the general formula (I) below which are useful as disperse dyes.

R ¹ represents a substituted or unsubstituted unsaturated aromatic group of the general formula

here,

R ² represents C ₁ -C ₄ alkyl,

R ³ represents C ₁ -C ₄ alkyl or alkoxy,

X represents a halogen atom.

The present invention also relates to a method for producing the heterocycle compound of the general formula (I). The heterocycle compound of the general formula (I) may be prepared by reacting a compound of the general formula (II) with a compound of the following structural formula (III) in a solvent and then slowly oxidizing with an oxidizing agent.

Wherein R ¹ is as defined above.

The α-chloro-α-substituted acetonitrile compound of formula (II) used as starting material in preparing the compound of formula (I) is a novel compound so far known as shown in Scheme 1 below. Likewise, the compound of formula (IV) may be obtained in high yield by adding the compound of cyanometal salt, triethylamine and tetrabutylammonium bromide to water and an organic solvent for 3 hours at a temperature range of -10 to 25 ° C. .

In the above formula,

R ¹ is as defined above,

R ⁴ represents C ₁ -C ₄ alkyl, tolyl, phenyl, chlorophenyl or bromophenyl.

On the other hand, as a solvent usable in the cyclization reaction for preparing the heterocycle compound of the general formula (I) in toluene, monochlorobenzene, 1,2-dichlorobenzene, 1,2-dichloroethane, dichloromethane and chloroform One selected may be mentioned and the reaction is carried out at a temperature of 50 to 150 ° C. The next step in which the cyclization reaction is carried out, oxidation, is carried out in the presence of oxidants such as chloranyl, persulfate, hydrogen peroxide and the like.

The present invention further relates to a method of dyeing or printing a fiber material using the compound of formula (I) according to the present invention, which method comprises contacting the fiber material with a heterocycle compound of formula (I). It is composed.

The compound of the general formula (I) is particularly useful for dyeing or printing hydrophobic fiber materials such as polyester, among fiber materials.

When used for dyeing or printing, the heterocycle compound of the general formula (I) according to the present invention is finely ground in an aqueous medium by lignin sulfonate or naphthalene sulfonate / formaldehyde condensate, etc., to prepare a liquid dye dispersion. This liquid dispersion can be used by itself or by drying with a spray dryer to be used for dyeing or printing textile materials in powder form.

As a dyeing method, a high-temperature dyeing method in which a hydrophobic fiber material is immersed in an aqueous salt bath and heated to a temperature of 105 ° C. or higher, preferably 110 to 140 ° C., ortho-phenylphenol, trichlorobenzene, or the like at a relatively high temperature such as boiling water One method selected from the carrier dyeing method for carrying out the dyeing in the presence of the carrier, and the thermosol method of padding the fiber material with an aqueous dispersion and then drying for 30 to 60 seconds at 170 to 210 ℃.

The printing can be carried out by mixing the aqueous dye dispersion with an appropriate stock paste to obtain a colored paste, padding the fibrous material and then steaming with hot steam or treating it with a thermosol. The fiber material may also be dyed by a solvent dyeing method in which an organic solvent such as trichloroethylene, perchloroethylene, or the like is used as the dyeing solution.

The dyeing or printing thus obtained is preferably subjected to well-known post-processing treatments such as softening, waterproofing, tactile improvement, antistatic processing, sanitary processing, and the like, in particular by using the heterocycle compound of general formula (I) Polyester fiber materials dyed or printed by conventional methods are excellent in various fastnesses such as light fastness, sublimation fastness and wet fastness, and these properties are not degraded even after heat setting and post processing.

The textile material is dyed with a high concentration of dyes to give a dye of a deep color (eg JIS 2/1), which has excellent wash fastness and heat setting of the dyeing compared to the dyeing with conventional disperse dyes. It maintains better properties even after treatment. In view of the recent high demand of consumers for the fastness of washing, it is very important to show the excellent fastness of washing.

On the other hand, since the heterocycle compound of the general formula (I) exhibits excellent properties also in dyeing ability such as dyeing power and build-up property, deep color dyeing or printing can be easily obtained by a particularly high temperature dyeing method. In addition, the compounds of the present invention may be used in combination with other dyes in order to enhance their performance, whereby various colors may be obtained.

Considering the properties of the general formula (I) heterocycle compound as mentioned above, this compound is usually required to be dyed in a deep color and should be frequently washed, especially for dyeing clothes such as sportswear which requires excellent washing fastness. It is contemplated that this may be preferably used.

Hereinafter, the present invention will be described in more detail based on the following examples. However, these examples are only for the understanding of the present invention, and the scope of the present invention in any sense is not limited to these examples.

Example 1

To 20 g of water and 60 ml of toluene, 20.5 g of 2-chloro-7-methyl-3-quinoline carboxaldehyde, 4 g of triethylamine, 1.0 g of tetrabutylammonium bromide and 7.4 g of sodium cyanide were added, followed by cooling to -5 ° C while stirring. I was. A mixed solution of 13.8 g of methanesulfonyl chloride and 60 ml of toluene was added dropwise at a temperature range of −5 to 0 ° C. for 3 hours, and then heated to room temperature with stirring. After leaving the reaction mixture at room temperature for 30 minutes, the resulting water layer was discarded, the organic layer was dried and distilled under reduced pressure to obtain α-chloro-α- (2-chloro-7-methyl-3-quinolyl) acetonitrile of the following structural formula. Obtained in% yield.

Example 2

The following structural formulas were carried out in the same manner as in Example 1, except that 20.9 g of 9-methyl-2-carbazolecarboxaldehyde was used instead of 20.5 g of 2-chloro-7-methyl-3-quinoline carboxaldehyde. Α-chloro-α- (9-methyl-2-carbazole) acetonitrile compound was obtained in a yield of 80%.

Example 3

12.0 g of the compound prepared in Example 1, 11.3 g of the compound of formula (III), and 9.5 g of para-toluenesulfonic acid monohydrate were added to 60 ml of toluene, heated to 90 to 95 ° C, and reacted for 2 hours. 9 g of ammonium persulfate was added to the reaction mixture, followed by further stirring for 1 hour to complete the oxidation reaction, and the mixture was cooled to 10 ° C while slowly adding 80 ml of methanol. The cooled mixture was filtered, washed with 50 ml each of methanol and water and dried to give pure benzodifuranone dye of the following structural formula in 72% yield. This compound exhibited a bright red color when dissolved in dimethylformamide and lambda max was measured at 503 nm.

Example 4

Except for using 12.1 g of the compound obtained in Example 2 instead of the compound of Example 1 in the same manner as in Example 3 to obtain a compound of the following structural formula in 70% yield. This compound showed a bright navy blue color when dissolved in dimethylformamide.

[Examples 5 to 8]

The benzodifuranone compound according to the present invention was obtained by the same method as in Example 3, and the prepared compound is shown in Table 1 below.

Claims (12)

Heterocycle compound of the following general formula (I). Wherein R ¹ represents a substituted or unsubstituted unsaturated aromatic group of the general formula Wherein R ² represents C ₁ -C ₄ alkyl, R ³ represents C ₁ -C ₄ alkyl or alkoxy and X represents a halogen atom. A process for preparing a heterocycle compound of the following general formula (I), characterized by reacting a compound of the general formula (II) with a compound of the following structural formula (III) in a solvent and then oxidizing with an oxidizing agent. Wherein R ¹ is as defined in claim 1. The method of claim 2, wherein the oxidant is one selected from chloranyl, persulfate, and hydrogen peroxide. The method according to claim 2, wherein the solvent is one selected from toluene, monochlorobenzene, 1,2-dichlorobenzene, 1,2-dichloroethane, dichloromethane and chloroform. The process of claim 2 wherein the reaction is carried out at a temperature of 50 to 150 ° C. Intermediate compound of the following general formula (II). Wherein R ¹ is as defined in claim 1. A method of preparing the compound of formula (II), wherein the compound of formula (IV) is reacted with cyanometal salt, triethylamine and tetrabutylammonium bromide in water and an organic solvent. Wherein R ¹ is as defined in claim 1. The process of claim 7 wherein the reaction is carried out at a temperature of −10 to 25 ° C. 9. A method of dyeing or printing a textile material using the compound of formula (I) according to claim 1 as a dye. The method of claim 9 wherein the fibrous material is a hydrophobic polyester. 10. The process according to claim 9, wherein the compound of formula (I) is prepared and used as a liquid dye dispersion together with lignin sulfonate or naphthalene sulfonate / formaldehyde condensate. The method according to claim 9, which is performed by one method selected from high temperature dyeing method, carrier dyeing method, and thermosol method.