JPH0334501B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on formula (1) [During the ceremony,

[Formula] is halogen, nitro, C ₁ - C ₄ alkyl, C ₁ - _{C 4} alkoxy, cyano, -OH, -COOR, -SO ₂ R, -SO ₂ NHR or

[Formula] may be substituted. (However, R and R' are the same or different C ₁ to _{C 4}
(indicates alkyl). or

[Formula] may be substituted with halogen, _C1 - _C4 alkyl or _C1 - _C4 alkoxy. n is 0 or 1], a method for producing the same, and a method for coloring an organic polymer material using the same. The compounds of formula (1) of the present invention are new. The present inventor has discovered that the compound of formula (1) gives organic polymeric materials a robust orange color.
It was discovered that it can be dyed, printed or colored red. The present invention will be explained in detail below. The compound represented by formula (1) is a compound of formula (1) prepared separately by diazotizing the above amines with sodium nitrite in an aqueous mineral acid solution such as hydrochloric acid or sulfuric acid, or with nitrosyl sulfuric acid in sulfuric acid.

It can be obtained by quickly pouring the compound of formula (3) into an alkaline solution and causing coupling. The compound of formula (3), which is a coupling component, has the formula The compound is heated to -5 to 5°C, preferably -3 to 0, using a dehydrating agent such as phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, or thionyl chloride in an inert organic solvent such as dimethylformamide, formamide, or N-methylpyrrolidone. Obtained by dehydration at °C. In addition, the compound (1) is obtained by diazotizing the compound of formula (2), which is a diazo component, by the method described above, and coupling it with the compound of formula (5) on the alkali side. [During the ceremony

【formula】

[Formula] n has the same meaning as in the above formula (1). ] After obtaining the compound, this azo compound is converted to the above formula (5).
It can also be obtained by dehydrating the compound using the same method as that used for dehydrating the compound. Formula (2) which is the diano component of the compound of formula (1) of the present invention
When n=0, the compound includes aniline, and its monosubstituted anilines include nitroanilines such as 0-nitroaniline, m-nitroaniline, or p-nitroaniline, 0-chloroaniline, m-chloroaniline. , p-chloroaniline, 0-promaniline, m-promaniline or p-bromaniline, 0-toluidine, m-toluidine, p-
Anilines substituted with lower alkyl such as toluidine, 0-ethylaniline or p-ethylaniline, 0-anisidine, m-anisidine, p-
Lower alkoxy-substituted anilines such as anisidine, 0-phenetidine, m-phenetidine or p-phenetidine, cyano-substituted anilines such as p-cyanoaniline, 0-aminophenol, m-
Aminophenols such as aminophenol or p-aminophenol, p-aminobenzoic acid methyl ester, p-aminobenzoic acid ethyl ester, p-aminobenzoic acid propyl ester or p-aminobenzoic acid ethyl ester;
-lower alkyl esters of aminobenzoic acid, such as aminobenzoic acid butyl ester, 3-(N-
Sulfamoyl groups such as methylsulfamoyl)-aniline, 3-(N-ethylsulfamoyl)-aniline, 3-(N,N-dimethylsulfamoyl)aniline, 3-(N,N-diethylsulfamoyl)aniline Examples of anilines substituted with 2,4-dichloroaniline, 2,5-dichloroaniline, 2,4,6-trichloroaniline, 2,4,5-trichloroaniline, 2-chloro-4-nitroaniline, 2-cyano-4-nitroaniline, 2-methyl-5-nitroaniline,
2-Methyl-4-nitroaniline, 2-methoxy-4-nitroaniline, 2,6-dichloro-4-
Nitroaniline, 2-nitro-4-methoxyaniline, 2-methoxy-5-chloroaniline, 3-
Examples include amino-4-methoxyphenylmethylsulfone. In addition, in the case of n=1, aminoazonezenes such as aminoazonezene, 4-(2-
Nitrophenylazo)aniline, 4-(3-nitrophenylazo)aniline, 4-(4-nitrophenylazo)aniline, 4-(2-chlorophenylazo)aniline, 4-(2-methylphenyl) azo)aniline, 4-(3-methylphenylazo)
Aniline, 4-(2-methylphenylazo)aniline, 4-(4-hydroxyphenylazo)aniline, 4-(4-carbomethoxyphenylazo)
Aniline, 4-(3-methylsulfonylphenylazo)aniline, 4-(4-cyanophenylazo)
Aniline, 2-methyl-4-(2-methylphenylazo)aniline, 2,5-dimethoxy-4-
Examples include (4-carbomethoxyphenylazo)aniline and 2,5-dimethoxy-4-(4-nitrophenylazo)aniline. The water-insoluble azo compound of formula (1) of the present invention is suitable for dyeing or printing polymeric organic materials such as synthetic fibers, especially fibers such as polyester cellulose acetate, cellulose triacetate, or acrylic, and produces a fast orange to red dyed product. is obtained. In this case, it is preferable to use a dyeing composition prepared by dispersing the azo compound of formula (1) with a dispersant and mixing it with other dyeing aids if necessary. That is, the monoazo dye may be treated with an anionic dispersant such as a formalin condensate of naphthalene sulfonic acid, sulfated creosote oil, or lignin sulfonic acid, or a nonionic dispersant such as a block copolymer of ethylene oxide and propylene oxide, or an ethylene oxide adduct of alkylphenol. The dye composition is prepared by sufficiently wet grinding using a ball mill or sand mill in the presence or absence of an activator and a small amount of water, or by further spray drying. This composition is used for conventional high-temperature dyeing, carrier dyeing, thermosol dyeing, and textile printing. In the case of textile printing, it is desirable to use a natural sizing agent, a synthetic sizing agent, a PH regulator, and a deep dyeing agent together. Discharge printing can also be carried out by printing a paste containing a discharge printing agent such as tin chloride, Rongarit or alkali, then overprinting a colored paste containing the main dye and steaming. The compound of formula (1) of the present invention can also be used in organic polymeric materials such as polypropylene, polyethylene, polyamide, polyester, polystyrene,
Phenol resins, amino resins, copolymers of styrene and acrylonitrile, methacrylonitrile, etc. can be colored. In other words, organic polymer material pellets etc.
The compound of formula (1) is mixed uniformly, heated, and fed to a suitable extruder, molding machine, fiber spinning machine, etc., or the compound of formula (1) is mixed uniformly, heated, and fed to a suitable extruder, molding machine, fiber spinning machine, etc. After the compound is added, heated, and mixed uniformly, it can be applied to any molding machine to obtain an orange to red colored product. This will be explained below by giving examples. All references to "Example Middle" refer to parts by weight. Example 1 Add 4.7 parts of aminoazobenzene hydrochloride and 3.1 parts of hydrochloric acid to 31 parts of water, stir for 1 hour, then add 35 parts of water, continue stirring for about 30 minutes, and add 1.5 parts of sodium nitrite while adding 11 parts of ice. Pour the solution dissolved in 2 parts of water and heat to 10°C.
Keep for 1.5 hours. The diazo solution was mixed with 3-oxy-
2-cyanonaphthalene 3.4 parts, caustic soda 1.5 parts,
2 parts soda carbonate, 1.7 parts sodium bicarbonate, water
Quickly add it to a solution consisting of 150 parts at 10℃ or less,
After stirring for an hour, adjust the pH of the solution to 4 with 6.9 parts of hydrochloric acid, heat it to 60°C, keep it for 1 hour, filter, and wash with water. 7.0 parts of crystals of a compound represented by the following formula were obtained.
This one has a λmax of 540nm (75% acetone solvent) m.
The temperature was p.226-229℃. Example 2 2.8 parts of p-nitroaniline was added to 12 parts of water and 5.5 parts of hydrochloric acid, and after stirring for 30 minutes, 9.2 parts of ice was added, and thereto,
Pour a solution prepared by dissolving 1.4 parts of sodium nitrite in 2.1 parts of water and keep at 0-2°C for 2 hours. 3 of the diazo liquid
- Add quickly at below 5°C to a solution consisting of 3.8 parts of oxy-2-naphthoic acid amide, 1.5 parts of caustic soda, 2 parts of soda carbonate, 1.7 parts of sodium bicarbonate, and 150 parts of water, continue stirring for 2 hours, and then filter. Dry. The obtained powder was dissolved in 60 parts of DMF, and 3.5 parts of phosphorus oxychloride was added to the solution at -3-0°C.
The temperature was kept at the same temperature for 4 hours, and the precipitated crystals were filtered off. 7.1 parts of crystals of a compound represented by the following formula were obtained.
The λmax of this product was 520 nm (75% acetone solvent) mp 291-293°C. Example 3 Three parts of the dye shown in Example 1 was added to Demol N6.
Part (dispersant manufactured by Kao Atlas Co., Ltd.) Demol C6 part (dispersant manufactured by Kao Atlas Co., Ltd.) was treated in a wet state for 5 hours to obtain a finely divided dye. This finely divided dye
Disperse 0.1 part in 100 parts of water and pH it with acetic acid.
After preparing 5, add 5 parts of cloth made of polyester fiber, keep it under pressure at 130℃ for 60 minutes, take it out, wash with water, and add 2 parts of caustic soda in 1000 parts of water.
Reduction cleaning was performed at 80°C for 15 minutes with 100 parts of a solution containing 2 parts of hydrosulfite and 1 part of Monogen (manufactured by Daiichi Kogyo Yakuhin). After that, it was washed with water and dried. A vivid red dyed product with a bluish tinge was obtained, and this product had excellent light fastness, sublimation fastness, and fastness after post-processing. Example 4 0.2 part of the compound obtained in Example 1 is mixed with 200 parts of polypropylene (manufactured by Chitsuso) and rotated with a rotary mixer. Next, this surface-coated polypropylene resin was melt-kneaded at 200°C and molded using an injection molding machine.
This molded product had a clear red hue, and the pigment showed very little discoloration or fading even when melted at 250°C. Examples 5-44 Compounds of formula (1) as defined in the following table were prepared by the method of Example 1 or 2. The following table shows the color tone when polyester fibers and resins are colored using the same. There was no significant difference in color tone between the cases in which polyester fibers were colored and the cases in which polyethylene, polypropylene, and vinyl chloride resins were colored.

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Claims (1)

[Claims] 1 formula [Wherein, [Formula] is halogen, nitro, C ₁ to C ₄ alkyl, C ₁ to C ₄ alkoxy, cyano,
It may be substituted with -OH, -COOR, -SO ₂ R, -SO ₂ NHR or [Formula] (provided that R and R' represent the same or different C ₁ -C ₄ alkyl). [Formula] may also be substituted with halogen, _C1 - _C4 alkyl, or _C1 - _C4 alkoxy. n is 0 or 1. ] Water-insoluble azo compound. 2 formulas [In the formula, [formula] is halogen, nitro, C ₁ to C ₄ alkyl, C ₁ to C ₄ alkoxy, cyano, -
It may be substituted with OH, -COOR, _-SO2R , _-SO2NHR or [Formula]. (However, R and R' represent the same or different C ₁ to C ₄ alkyl.) Also, [Formula] may be substituted with halogen, C ₁ to C ₄ alkyl, or C ₁ to _{C 4} alkoxy. good. n is 0 or 1] is dehydrated by the action of a dehydrating agent in an inert solvent. A method for producing a water-insoluble azo compound represented by the following formula: [Formula] [Formula] and n have the same meanings as above. 3 formulas [In the formula, [formula] is halogen, nitro, C ₁ to C ₄ alkyl, C ₁ to C ₄ alkoxy, cyano, -
It may be substituted with OH, -COOR, _-SO2R , _-SO2NHR or [Formula]. (However, R and R' represent the same or different C ₁ to C ₄ alkyl.) Also, [Formula] may be substituted with halogen, C ₁ to C ₄ alkyl, or C ₁ to _{C 4} alkoxy. good. n is 0 or 1. ] A method for coloring a polymeric organic material, which is characterized by using a water-insoluble azo compound shown in the following.