JPH0676385B2 - Anthrapyridone-based compound, production method and use thereof - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to an anthrapyridone compound, a method for producing the same, and a colorant for resins using the same.

[Prior art]

Conventionally, an anthrapyridone compound has been used as a colorant for synthetic resins, and specifically, an anthrapyridone compound represented by the following structural formula is known. However, although these colorants have a characteristic that they are excellent in heat resistance, resin molded products colored with these colorants do not have sufficient performance such as light resistance, bleed resistance and elution resistance, Further improvements were requested.

[Problems to be Solved by the Invention]

The present invention, when the specific anthrapyridone-based compound obtained by the present invention is used as a colorant for a resin, the colorant has excellent heat resistance, and has good light resistance, bleeding resistance, elution resistance, etc. That is, the present invention has been completed. Therefore, the main object of the present invention is to provide a colorant having such excellent performance.

[Means for solving problems]

The present invention has the general formula [I] (In the formula, X represents -NHCOR ¹ , -CONR ² R ³ , -COR ⁴ , -SO ₂ R ⁵ or -SO ₂ NR ⁶ R ⁷ , R ¹ and R ⁴ are lower alkyl groups, R ² and R ³ Is H or a lower alkyl group, R ⁵ is a lower alkyl group or a hydroxyethyl group, and R ⁶ and R ⁷ are each independently a hydrogen atom or a lower alkyl group. The colorant for resin using is the gist. The anthrapyridone compound represented by the general formula [I] used in the present invention can be produced by the following method. That is, the following structural formula [II] Α-haloanthrapyridone represented by the following general formula [II
I] (In the formula, X has the same meaning as defined above.) An amine represented by is reacted in an organic solvent, preferably in the presence of metallic copper or a copper compound, preferably at a temperature of 100 ° C to 170 ° C. It can be manufactured. At this time, a deoxidizer may be added. Further, as another manufacturing method, the general formula [II] Α-haloanthrapyridone represented by the following general formula [II
I] (In the formula, X has the same meaning as defined above.) By reacting with an amine represented by the following formula: (In the formula, X has the same meaning as defined above.), And then the compound is obtained by hydrolysis. In the anthrapyridone compound represented by the above general formula [I] of the present invention, the lower alkyl group means a C _{1 to} C ₄ linear or branched alkyl group. Further, as the copper compound that can be used in the production method of the present invention, cuprous chloride, cuprous halide such as cupric chloride, copper oxide, copper sulfate, copper acetate, and the like, these can be used alone or Can be used together. Further, examples of the organic solvent include halobenzene such as monochlorobenzene and orthodichlorobenzene, alkylbenzene such as toluene and xylene, polar solvent such as dimethylformamide, sulfolane and dimethylsulfoxide, and these solvents can be used alone or in combination. . Examples of the deoxidizing agent include alkali metal salts such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, sodium acetate and the like. Resins that can be used for resin coloring, which is the main object of the present invention, include polystyrene, polymethyl methacrylate, polyvinyl chloride, acrylonitrile butadiene.
Styrene copolymer (ABS resin), acrylomitryl-styrene copolymer (AS resin), polycarbonate, polyphenylene oxide, polypropylene, polyethylene,
Polyacrylonitrile, polyamide, polyacetal,
A thermoplastic resin such as polyethylene terephthalate or polybutylene terephthalate, or a phenol resin,
The thermosetting resin such as urea resin, melamine resin, unsaturated polyester resin, epoxy resin or diallyl phthalate resin can be used. The colorant of the present invention is obtained by mixing the resin and the colorant by an appropriate method,
A colored product can be obtained by a method such as injection molding, extrusion, or spinning by applying heat or pressure. A known method can be used for coloring the resin. For example, resin pellets or powders are mixed in a suitable mixer with the ground colorant and various additives as necessary, and then the colorant is dissolved in the resin with a kneader, roll mill, Banbury mixer, extruder, etc. Alternatively, it can be dispersed and colored. If necessary, molding such as compression, injection, extrusion and blow can be performed to obtain a molded product. It is also possible to add a colorant to a monomer containing an appropriate polymerization catalyst to form a desired thermoplastic resin or thermosetting resin colored product by polymerization, and mold it by an appropriate method. The amount of the colorant added is not particularly limited, but from the viewpoint of economic efficiency, it is 0.01 to 5% by weight, preferably 0.01 to 1% by weight with respect to the resin.
Used in weight percent. Further, it is also possible to use other dyes and pigments which are commonly used for coloring resins. For example, titanium dioxide is 0.
It is also possible to obtain an opaque colored molded product by using together 1 to 1% by weight.

【Example】

Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples.
In the examples, parts represent parts by weight. Example 1 The following structural formula 4-bromo-1,9-N-methylanthrapyridone represented by 3.
4 parts and the following structural formula With 15 parts of the amine represented by the formula (1) in the presence of 0.1 part of copper acetate and 2.0 parts of sodium acetate in orthodichlorobenzene as a solvent at a temperature of 130 to 140 ° C. for 20 hours, and the formed precipitate is separated by filtration. , Washed with methanol and dried to obtain the following structural formula 2.8 parts (68% yield) of a cake of the anthrapyridone compound represented by This compound showed a single red spot by thin layer chromatography, and FD-Mass showed a peak at 409, which was the same as the theoretical molecular weight. The λmax (chloroform) of this compound was 535 nm. Next, 0.2 part of the obtained anthrapyridone compound was added to ABS resin.
After mixing with 100 parts, coloring was performed at 205 ° C. using an extruder to obtain colored pellets. The colored pellets were molded by an injection molding machine at a cycle of 230 ° C. for 1 minute to obtain a transparent bluish red plate-shaped colored molded product. The obtained plate-shaped colored molded product had excellent bleeding resistance, elution resistance, and light resistance. Further, even when injection molding was carried out at a cycle of 270 ° C. for 3 minutes, the change in hue of the plate-like colored molded product was slight and the heat resistance was good. Example 2 Instead of the amine used in Example 1, the following structural formula Acetoanilide compound 4.8 parts and copper acetate 0.1
Parts, 2.1 parts of sodium hydrogencarbonate in the presence of orthodichlorobenzene solvent at a temperature of 145 ℃ ~ 150 ℃ for 18 hours, the precipitate formed was filtered off, washed with methanol and dried to obtain a yellowish product. 3.7 parts of cake in 1% 5% caustic soda water
After reacting at 30-135 ° C for 20 hours, separating by filtration, washing with water, and drying, the following structural formula 3.2 parts of an anthrapyralidone compound represented by (yield 70
%) Was obtained. This compound showed a single red spot by thin-layer chromatography, and PD-Mass had a peak at 459, which was the same as the theoretical molecular weight. The λmax (chloroform) of this compound was 534 nm. The obtained compound (0.2 part) was molded according to the method described in Example 1 to obtain a yellowish red plate-shaped colored molded product. The obtained plate-shaped molded product was excellent in bleed resistance, elution resistance and light resistance. Also, as in Example 1, the heat resistance was excellent. Example 3 The formula used in Example 1 according to the method described in Example 1. Instead of the amine represented by In the same manner, using the amine shown in An anthrapyridone compound represented by This compound showed a single red spot by thin layer chromatography, and FD-Mass had a peak at 430, which was the same as the theoretical molecular weight. The λmax (chloroform) of this compound was 533 nm. The obtained compound (0.2 part) was molded according to the method described in Example 1 to obtain a yellowish red plate-shaped colored molded product. The obtained plate-shaped molded product was excellent in bleed resistance, elution resistance and light resistance. Also, as in Example 1, the heat resistance was excellent. Example 4 According to the method described in Example 1, the amine used in Example 1 was replaced with the following structural formula. In the same manner as above, the following structural formula is used. The anthrapyridone compound represented by This compound showed a single red spot by thin layer chromatography, and FD-Mass had a peak at 459, which was the same as the theoretical molecular weight. The λmax (chloroform) of this compound was 534 nm. The obtained compound (0.2 part) was molded according to the method described in Example 1 to obtain a yellowish red plate-shaped colored molded product. The obtained plate-shaped molded product was excellent in bleed resistance, elution resistance and light resistance. Also, as in Example 1, the heat resistance was excellent. Comparative Examples 1, 2, 3 The results of comparison with the compound of the present invention using the known compounds A to C are shown below. Comparative Example 1 ...... When using the known compound A Comparative example 2 ………… Known compound B 〃 Comparative example 3 ………… Known compound C 〃 Known compound 0.2 parts each was used and described in Example 1. Each was molded according to the above method. The quality of the obtained molded product is compared with that of the anthrapyridone compound of the present invention.
Shown in. As is clear from Table 1, the anthrapyridone compound of the present invention has excellent heat resistance, and the colored resin molded product has good light resistance, bleed resistance and elution resistance. . ☆ Bleed resistance A soft PVC board containing 1.0% TiO ₂ is overlaid with an ABS colored molded board, and treated at 80 ° C for 2 hours under a load of 100g / cm ² to create a soft PVC board.
The degree of coloration on the plate was evaluated by a JIS-L-0805 stain gray scale. ☆ Elution resistance Tested and evaluated according to the test method for coloring materials of the Hygiene Council such as polyolefin-dissolution test method. ○: No elution ×: Elution in the solvent shown in (). ☆ Light resistance According to JIS-L-0842, accelerated test was performed with a fade meter. Judgment was performed using a blue scale that was simultaneously irradiated. ☆ Colored pellets obtained from heat resistant ABS resin are 230 ℃ × 1 by injection molding machine
The heat resistance was evaluated by judging the degree of discoloration of the one molded by the minute cycle at 270 ° C. for 3 minutes using the standard molded product by the minute cycle with the JIS-L-0804 discoloration glaze scale. Example 5 Structural formula according to the method described in Example 1 An anthrapyridone compound represented by This compound showed a single red spot by thin layer chromatography, and FD-Mass had a peak at 394, which was the same as the theoretical molecular weight. The λmax (chloroform) of this compound was 531 nm. Next, 0.2 parts of the obtained compound was mixed with 100 parts of a polystyrene resin, and then colored at 205 ° C. using an extruder to obtain a colored pellet. The colored pellets were molded by an injection molding machine at a cycle of 220 ° C. for 1 minute to obtain a bluish red molded product. The obtained molded product was excellent in bleed resistance, elution resistance and light resistance. Example 6 The following structural formula was used according to the method described in Example 1. An anthrapyridone compound represented by The compound obtained had a λmax (chloroform) of 526 nm. Next, 0.1 parts of the obtained compound was mixed with 100 parts of polyethylene resin, and then colored at 220 ° C. using an extruder to obtain colored pellets. The colored pellets were molded according to the method described in Example 1 to obtain a bluish red plate-shaped colored molded product. The plate-shaped molded product obtained was excellent in bleed resistance and light resistance. Examples 7 to 14 Molded by the method described in Example 1 using the anthrapyridone compounds shown in Table 2 as a colorant for resins. The obtained molded product was excellent in bleed resistance, elution resistance and light resistance. Also, as in Example 1, the heat resistance was excellent. General formula [I]

Claims (4)

[Claims] 1. A general formula [I] (In the formula, X represents -NHCOR ¹ , -CONR ² R ³ , -COR ⁴ , -SO ₂ R ⁵ or -SO ₂ NR ⁶ R ⁷ , R ¹ and R ⁴ are lower alkyl groups, R ² and R ³ is H
Or a lower alkyl group, R ⁵ represents a lower alkyl group or a hydroxyethyl group, and R ⁶ and R ⁷ each independently represent a hydrogen atom or a lower alkyl group. ) An anthrapyridone compound represented by: 2. General formula [II] Α-haloanthrapyridone represented by the following general formula [II
I] (In the formula, X represents -NHCOR ¹ , -CONR ² R ³ , -COR ⁴ , -SO ₂ R ⁵ or -SO ₂ NR ⁶ R ⁷ , R ¹ and R ⁴ are lower alkyl groups, R ² and R ³ is H
Or a lower alkyl group, R ⁵ represents a lower alkyl group or a hydroxyethyl group, and R ⁶ and R ⁷ each independently represent a hydrogen atom or a lower alkyl group. ) The general formula [I] characterized by reacting with an amine represented by (In the formula, X has the same meaning as defined above.) A method for producing an anthrapyridone compound. 3. General formula [II] Α-haloanthrapyridone represented by the following general formula [II
I] (In the formula, X represents -NHCOR ¹ , -CONR ² R ³ , -COR ⁴ , -SO ₂ R ⁵ or -SO ₂ NR ⁶ R ⁷ , R ¹ and R ⁴ are lower alkyl groups, R ² and R ³ is H
Or a lower alkyl group, R ⁵ represents a lower alkyl group or a hydroxyethyl group, and R ⁶ and R ⁷ each independently represent a hydrogen atom or a lower alkyl group. ) Is reacted with an amine represented by the general formula [V] (Wherein, X has the same meaning as defined above), and the compound is then hydrolyzed. (In the formula, X has the same meaning as defined above.) A method for producing an anthrapyridone compound. 4. A general formula [I] (In the formula, X represents -NHCOR ¹ , -CONR ² R ³ , -COR ⁴ , -SO ₂ R ⁵ or -SO ₂ NR ⁶ R ⁷ , R ¹ and R ⁴ are lower alkyl groups, R ² and R ³ is H
Or a lower alkyl group, R ⁵ represents a lower alkyl group or a hydroxyethyl group, and R ⁶ and R ⁷ each independently represent a hydrogen atom or a lower alkyl group. ) An anthrapyridone compound represented by