JPS5812903B2 - Koubunshizairiyounochiyakushiyokuhouhou - Google Patents

Description

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

The purpose of the present invention is to color molded products such as film sheets, pipes, fibers, etc. made of polymeric materials in a yellow tone with excellent fastness, and it is based on the general formula [■] [where A is a non-ionized substituent]. A phenylene group, a naphthyl group, and rings B and C in which two optionally substituted carbonyl groups are bonded at the ortho or peri position may be substituted with a halogen atom.

] This can be achieved by using the compound shown below.

The compound used in the present invention may form a resonance structure as shown in the following formula, but in the present invention, the structural formula represented by the general formula [■] includes all of the general formulas [■a], [■], and [■ b].

This compound is a novel compound and can be produced, for example, by a pulling down method.

That is, it is represented by the following formula (■) [In the formula, A is a phenylene group or naphthylene group, which may be substituted with non-ionizing substitution and in which two carboxyl groups (carbonyl groups) are bonded at the ortho or peri position] Dicarboxylic acids or their carboxylic acid anhydrides are represented by the following general formula (■) [In the formula, rings B and C may be substituted with halogen atoms.

] It can be produced by carrying out a heating reaction with a quinoline derivative represented by the following formula.

Alternatively, without isolating the compound represented by the general formula [■], for example, 8-amino-quinaldine and 1 represented by the following formula (■) or (in the formula, rings B and C may be substituted with halogen atoms)・After reacting 8-naphthalene dicarboxylic acids or their acid anhydrides under heating, the general formula (II, l
It can be produced by adding dicarboxylic acids represented by or an acid anhydride thereof and carrying out a heating reaction.

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

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

In the coloring method of the present invention, the polymer materials to be colored include polyolefin-based, polystyrene-based, polyacrylonitrile-based, polyacrylate, polyvinyl chloride-based,
Materials include polyacetal, polyamide, polycarbonate, amine resin, cellulose acetate, epoxy resin, and polyester.

To carry out the present invention, the required amount of the compound represented by the above general formula [■] is blended into a polymeric material and/or heated and kneaded, and the compound is then molded using a compression molding method, an injection molding method, a calendar molding method, an extrusion molding method, etc. Films, sheets,
Molded products such as pellets can be colored with fibers and pulp.

Coloring can also be carried out by a cast molding method in which a compound represented by the general formula [■] is blended into a liquid monomer or prepolymer and then polymerized and cured.

The polymeric material colored by the coloring method of the present invention exhibits excellent heat resistance, light resistance, and vivid coloring properties, and has better effects than conventional coloring pigments.

Next, examples will be shown.

"Parts" in Examples are "parts by weight."

Example 1 0.2 part of quinophthalone pigment represented by the following structural formula was blended with 200 parts of polystyrene resin, and 2 parts were mixed with 200 parts of polystyrene resin 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, no change in color tone was observed depending on the injection conditions.

When this molded plate was irradiated with light using a weather meter, no discoloration or fading was observed, and it was judged to be grade 6 or higher on a blue scale.

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

338 parts of 8-naphthaliminoquinaldine, 286 parts of tetrachlorophthalic anhydride, 40 parts of zinc chloride and 2000 parts of trichlorobenzene are reacted at the boiling point under reflux for 3 hours, then 500 parts of dimethylformamide is added and stirred under reflux for 1 hour. .

After cooling, the yellow reaction product is washed with 1000 parts of dimethylformamide and finally with ethanol.

After drying, a yellow pigment having a melting point of 360° C. or more and a maximum absorption near 444 mμ in the visible spectrum is obtained.

The results of elemental analysis were as shown below and almost agreed with the calculated values.

Further, a polystyrene resin was colored in the same manner as above using a quinophthalone pigment having the following structural formula, and injection molded under the conditions shown in Table 1 above to obtain a molded plate.

Almost no change in color tone was observed depending on the injection conditions.

Example 2 3 parts of the quinophthalone pigment represented by formula (1-1) used in Example 1 was blended with 2000 parts of polycarbonate resin.
Melt extrusion was performed at 60 to 265°C to obtain pellets colored yellow.

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

This molded plate showed no discoloration or fading when irradiated with light using a weather meter, and was judged to be grade 6 or higher on a blue scale.

Example 3 1 part of a quinophthalone pigment represented by the following structural formula and 5 parts of rutile titanium oxide were blended with 1000 parts of ABS resin, and mixed and extruded using a melt extruder at 220 to 230°C to obtain pellets 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.

Further, even when this molded plate was irradiated with light using a weather meter, no discoloration or fading was observed, and it was grade 6 or higher as judged by blue scale.

Further, ABS resin was colored in the same manner as above using a quinophthalone pigment having the following structural formula, and injection molded under the conditions shown in Table 3 above to obtain a molded plate.

Almost no change in color tone was observed depending on the injection conditions.

Example 4 Two parts of a quinophthalone pigment represented by the following structural formula and di-(
300 parts of 2-ethylhexyl) phthalate was combined 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 5 0.6 parts of the quinophthalone pigment represented by the formulas (3-1) used in Example 3 and 3 parts of rutile titanium oxide were blended with 600 parts of polypropylene and mixed and extruded at 220 to 230°C using an extruder to give a yellow color. A colored pellet was obtained.

This pellet was injection molded under the conditions shown in Table 5 below to obtain a molded plate colored in bright yellow.

No change in color was observed depending on the injection conditions, and it showed excellent heat resistance.

Example 6 0.5 part of a quinophthalone pigment having the following structural formula was added to 500 parts of prepolymerized methyl methacrylate syrup, mixed, and the colored syrup was poured into a glass cell and heated at 50 to 70°C for 6 hours. After polymerizing at 100 to 120° C. for 3 hours, the mixture was cooled and peeled off to obtain a solid yellow polymethyl methacrylate resin plate.

Example 7 1 part of quinophthalone pigment similar to that used in Example 1, 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 this was mixed with 300 parts of glass fiber of isophthalic acid type. 240 parts of unsaturated 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 8 1 part of a quinophthalone compound having the following structural formula was uniformly dispersed in 3000 parts of water containing 3 parts of higher alkylbenzenesulfonic acid, 4 parts of o-phenylphenol was added, and 100 polyester fibers were immersed in this dyebath. 100℃
Staining was carried out for 2 hours at ~120°C.

After dyeing, the dyed product was washed with water and subjected to saw pink treatment at 70° C. for 20 minutes with 3,000 parts of water containing 4 parts of higher alcohol sulfate to obtain a yellow dyed product.

Polyester fibers were similarly dyed using a quinophthalone compound having the following structural formula to obtain a greenish-yellow dyed product.

Claims (1)

[Scope of Claims] 1 A polymeric material having the general formula [■] [wherein A is a halogen atom, a phenylsulfonyl group optionally substituted with a halogen atom, or a benzoyl group, Represents a phenylene group or naphthylene group in which two carbonyl groups are bonded at ortho or peri positions. Rings B and C may be substituted with halogen atoms. ] A method for coloring a polymeric material, characterized by coloring using a compound represented by the following.