JPS5813580B2 - Koubunshizairiyounochiyakushiyokuhouhou - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for coloring polymeric materials.

The purpose of the present invention is to color a polymeric material in a yellow tone with excellent fastness, which is represented by the general formula CI,1 [wherein A represents a lower alkyl group, phenyl group, -CONH2, and ring B is substituted with a halogen atom]. You can leave it there.

Z represents a phenylene group or naphthylene group in which two carbonyl groups are bonded at the ortho position and may be substituted with a nonionizable substituent.

The compound used in the present invention may form a tautomeric structure as shown in the following formula, and the structural formula represented by the general formula [■] in the present invention includes all of these general formulas (Ia, Ib).

This compound is a novel compound, and can be produced, for example, by the following method.

That is, the following formula [■] (In the formula, Z represents a phenylene group or a naphthylene group in which two carboxyl groups (carbonyl groups) are bonded at the ortho position, and may be substituted with a nonionizable substituent.

) or its carboxylic acid anhydride is represented by the following general formula (III) (wherein A is a lower alkyl group, a phenyl group, -CONH2
and ring B may be substituted with a /SS gene atom).

Moreover, without isolating the compound represented by the general formula (III, 1), for example, the following general formula [IV] [wherein A is a lower alkyl group, a phenyl group, -CONH2
2-methyl-8-aminoquinoline derivatives represented by the following formula (V) (in which ring B may be substituted with a halogen atom): It can also be produced by reacting with heating, and then adding dicarboxylic acids represented by general formula (II) or its acid anhydride and reacting.

In the method of the present invention, any compound produced by any method can be used as long as it is a compound represented by the above general formula [■].

Among the compounds used in the coloring method of the present invention, the following can be mentioned.

In the present invention, in addition to the above-mentioned compounds, the general formula CI)
The compounds shown above are used as pigments, but the above (
Compounds 1) to (16) are particularly preferably used.

Further, in the present invention, the effect can be further enhanced by using an antioxidant, ultraviolet rays, an inhibitor, etc. in combination.

Polymer materials used in the present invention include polyolefin, polystyrene, polyacrylonitrile, polyacrylate, polyvinyl chloride, polyacetal, polycarbonate, amine resin, cellulose acetate, and epoxy resin. , polyamide-based, polyester-based materials, etc.

In carrying out the present invention, coloring can be achieved by blending the required amount of the compound represented by the general formula (I) into a polymeric material.

For example, a polymer material containing the compound represented by the general formula [■] is heated and kneaded, and then formed into films, sheets, fibers, pipes, and pellets by ordinary molding methods such as compression molding, injection molding, and calendar molding. A molded product such as the above can be colored yellow, or it can be colored by a cast molding method in which a compound represented by the general formula [I] is blended with a liquid monomer or grepolymer and polymerized and cured.
As a coloring agent for paints, the general formula [■
] Coloring can also be achieved by blending a compound represented by the following formula.

In addition, polymer materials used in printing inks and general formula [I
By blending the compound represented by formula (I), it can be used as a coloring agent for ink.Furthermore, the compound represented by formula (I) can be used to color fibers and textiles by known dyeing methods.

The polymeric material colored by the coloring method of the present invention exhibits excellent heat resistance, light resistance, and vivid coloring properties, and has an extremely excellent coloring effect.

Next, examples will be shown.

Example 1 1.5 parts of monophthalone pigment represented by the following structural formula was blended with 1000 parts of polyethylene resin, and 2 parts were mixed using a melt extruder.
Mixed extrusion at 30°C yielded yellow colored pellets.

This pellet was injection molded under the conditions shown in Table 1 below to obtain a molded plate. At this time, there was almost no change in color tone depending on the injection conditions.
It showed better heat resistance than the compounds having 1 to 2).

Also, Table 10 No. When the molded plate molded under the conditions of 1 was irradiated with light using a weather meter, no discoloration or discoloration was observed, and it was grade 6 or higher according to the blue scale, and was certified by the Special Publication Publication No. 45-27.
It was found that the pigment exhibited better light resistance than the pigment having the following structural formula (1-3) produced by No. 343, and was also extremely excellent in solvent resistance and migration resistance.

The quinophthalone pigment used in this example was produced as follows.

86 parts of 2,4-dimethyl-8-aminoquinoline, 143 parts of tetrachlorophthalic anhydride, and 80 parts of trichlorobenzene
0 parts were mixed and reacted for 1.5 hours under reflux at the boiling point, 143 parts of tetraphthalic anhydride and 20 parts of zinc chloride were added, and the mixture was reacted for 4 hours under reflux.

Next, 300 parts of dimethylformamide was added and stirred for 1 hour under reflux heating. After cooling, the yellow reaction product was further washed with 600 parts of dimethylformamide (OMF) and finally with ethanol.

After drying, a yellow pigment with a melting point of 360° C. or higher was obtained.

The results of elemental analysis are shown in Table 2 below, and were almost in agreement with the calculated values.

Further, similar results were obtained by coloring and molding polyethylene resin under the same conditions as above using a quinophthalone pigment having the following structural formula.

Example 2 0.3 part of a quinophthalone pigment represented by the following structural formula was blended with 200 parts of a polystyrene resin, and pellets colored yellow were obtained by a melt extruder at 230°C.

This pellet was injection molded by a conventional method at a cylinder temperature of 240° C. to obtain a molded plate.

This molded plate was irradiated with light using a weather meter and judged by blue scale, and as a result, it was grade 6 or higher.

Example 3 3 parts of the quinophthalone pigment represented by the formula (1-1) used in Example 1 was blended with 1500 parts of polycarbonate to give 260 parts of polycarbonate.
Melt extrusion was performed at ~265°C to obtain yellow colored pellets.

This pellet was injection molded by a conventional method at a cylinder temperature of 280° C. to obtain a molded plate.

This molded plate was irradiated with light using a weather meter and judged by a blue scale, and as a result, it was grade 6 or above.

Example 4 2 parts of chimephthalone represented by the following structural formula, 5 parts of rutile titanium oxide, and 1 part of an ultraviolet inhibitor were mixed with 10 parts of ABS resin.
00 parts and mixed and extruded using a melt extruder at 220 to 230°C to obtain Beresoto colored yellow.

This pellet was injection molded under the conditions shown in Table 3 below to obtain a molded plate colored bright yellow.

At this time, no change in color tone was observed depending on the injection conditions.

Example 5 Two parts of ginophthalone pigment represented by the following structural formula and di(
300 parts of 2-ethylhexyl) phthalate was mixed with 700 parts of polyvinyl chloride resin, and then mixed with two rolls from 155 to
A yellow sheet with excellent migration resistance, heat resistance, and light resistance was obtained by kneading at 160°C.

Example 6 0.6 parts of the quinophthalone pigment represented by the formula (1-1) used in Example 1 and 3 parts of rutile titanium oxide were blended with 600 parts of polypropylene resin, and the mixture was mixed with 220-230 parts by an extruder.
Mixed and extruded at ℃, a yellow colored Beresoto was obtained.

This pellet was injection molded under the conditions shown in Table 4 below to obtain a molded plate colored in bright yellow.

At this time, no change in color due to injection conditions was observed, indicating excellent heat resistance.

Example 7 0.5 part of a quinophthalone pigment having the following structural formula was added and mixed with 500 parts of prepolymerized methyl methacrylate silasop, and this colored silasop was injected into a glass cell.
After polymerization at 100-120°C for 6 hours and 3 hours at 100-120°C, the mixture was cooled and peeled off to obtain a solid yellow polymethyl methacrylate resin plate.

Example 8 1 part of quinophthalone pigment having the following structural formula, 386 parts of calcium carbonate, 4 parts of zinc stearate, 25 parts of styrene monomer, and 35 parts of finely powdered polyethylene were mixed in a ball mill, and 300 parts of glass fiber was mixed with 300 parts of isophthalic acid-type non-polyethylene. 240 parts of saturated polyester resin and 10 parts of calcium hydroxide were mixed, a polymerization initiator was added, and the mixture was heated and molded at 180°C.

A reinforced polyester molded product colored bright yellow was obtained.

Example 9 1 part of a quinophthalone compound having the following structural formula was uniformly dispersed in 3000 parts of water containing 3 parts of higher sodium alkylbenzene sulfonate, 4 parts of 0-phenylphenol was added, and 100 parts of polyester fibers were added to the dyebath. Soak 100
Staining was carried out for 2 hours at ~120°C.

After dyeing, it was washed with water and soaped in 3,000 parts of water containing 4 parts of higher alcohol sulfate at 70°C for 20 minutes to obtain a yellow dyed product.

Claims (1)

[Claims] 1. A polymeric material represented by the general formula (I) [wherein A is a lower alkyl group, a phenyl group, -CONH2]
and ring B may be substituted with a halogen atom. Z represents a phenylene group or naphthylene group in which two carbonyl groups are bonded at ortho positions, and may be substituted with a halogen atom. ] A method for coloring a polymeric material, characterized by coloring using a compound represented by the following.