JPS5813579B2 - What is the best way to do this? - 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 molded products such as film sheets, pipes, and fibers made of polymeric materials in a yellow tone with excellent fastness. It may be substituted with an atom, a lower alkyl group, an alkoxy group, or a phenyl group.

X is a phenylene group or naphthylene group in which two carbonyl groups, which may be substituted with a nonionized substituent, are bonded at the ortho or peri position.

Rings Y and Z may be substituted with halogen atoms.

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

The compound used in the present invention may have a tautomeric structure as shown in the following formula, but in the present invention, the structural formula represented by the general formula [I] includes all of the general formula [1:Ia)C I][: Ib. l].

This compound is a new compound and can be produced, for example, by the method described below.

That is, the following general formula (II) [wherein X may be substituted with a nonionizable substituent,
A phenylene group or naphthylene group in which two carboxyl groups (carbonyl groups) are bonded at the or-1 position or the peri-position.

Dicarboxylic acids or dicarboxylic acid anhydrides represented by the following general formula (III) [In the formula, rings A and B may be substituted with a halogen atom, an alkino group, a phenyl group, or an alkoxy group.

Rings Y and Z may be substituted with halogen atoms.

] IJ is heated to react with a quinoline derivative represented by
It can be manufactured by

Alternatively, without isolating the compound represented by general formula CIII), for example, 8-aminoquinaldine and 1 or 2 represented by the following formula [■] [wherein Y and Z may be substituted with a halogen atom] - It can be produced by reacting naphthalene dicarboxylic acids or their dicarboxylic acid anhydrides under heating, then adding dicarboxylic acids represented by the general formula [■] or their acid anhydrides and carrying out the heating reaction.

In the method of the present invention, any compound represented by the above-mentioned general formula CI) can be used, regardless of the method by which it is produced.

Examples of the compounds used in the coloring method of the present invention include the following.

In the coloring method of the present invention, when particularly high migration resistance is required, those containing a halogen atom in the phenylene group or naphthylene group represented by X in general formula [I] are preferably used.

Polymer materials to be colored in the coloring method of the present invention include polyolefin, polystyrene, polyacrylonitrile, polyacrylate, polyvinyl chloride, polyacetal, polyamide, polycarbonate, amine resin, and cellulose acetate. Examples include epoxy resin type and epoxy resin type.

Paints and printing inks containing the above-mentioned polymeric materials can also be colored by the method of the present invention.

To carry out the present invention, the required amount of the compound represented by the general formula (I) is blended with a polymeric material and/or heated and kneaded, and then molded by compression molding, injection molding, calendar molding, or extrusion molding. Molded products such as films, sheets, fibers, pulp pellets, etc. can be colored using conventional molding methods.

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

Materials colored by the coloring method of the present invention exhibit vivid coloring properties with excellent heat resistance, light resistance, and chemical resistance, and have superior effects to conventional coloring pigments.

Next, examples will be shown.

In the examples, "parts" are "parts by weight".

Example l Quinophthalone pigment Q. represented by the following structural formula. 4 parts were blended with 200 parts of polystyrene resin, and 2 parts were mixed with 200 parts of polystyrene resin using a melt extruder.
Mixing and extrusion at 30°C gave a yellow colored beresotho.

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.

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

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

338 parts of 8-(1,2-naphthalene dicarboimino)-quinaldine, 286 parts of tetrachlorphthalic anhydride, 40 parts of zinc chloride and 2000 parts of trichlorobenzene were reacted under reflux at the boiling point for 3 hours, and then dimethylformamide 5
00 parts and stirred for 1 hour under reflux.

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

Melting point after drying: 360°C or higher, 444 mμ in visible spectrum
A yellow pigment is obtained which has an absorption maximum in the vicinity.

The results of elemental analysis were as follows, and were in close agreement 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.

No discoloration or fading was observed in this molded plate when exposed to light using a weather meter, and the blue scale rating was grade 6 or higher.

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 at 220 to 230'C using a melt extruder to obtain yellow colored pellets. .

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 graded 6 or above as judged by blue scale.

Example 4 Two parts of a quinophthalone 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 to 155 parts
The mixture was kneaded at ~160°C to obtain a yellow sheet with excellent migration resistance, heat resistance, and light resistance.

Example 5 06 parts of the quinophthalone pigment represented by the formula (3-1) used in Example 3 and 3 parts of rutile titanium oxide were blended into 600 parts of polypropylene, mixed and extruded at 220 to 230°C using an extruder, and colored yellow. Got a beret.

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

At this time, no change in color due to injection conditions was observed, indicating 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 for 3 hours at 100 to 120°C, 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 to this was added 300 parts of glass fiber and isophthalic acid. 240 parts of acid type unsaturated polyester resin, 10 parts of calcium hydroxide
A polymerization initiator was added to the mixture, 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 sodium alkylbenzene sulfonate, 4 parts of 0-phenylphenol was added, and 100 parts of polyester fibers were added to the dyebath. Soak 100
Stained for 2 hours at ~120°C.

After dyeing, it was washed with water and subjected to noping 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 structure to obtain a greenish-yellow dyed product.

Claims (1)

[Scope of Claims] 1. A polymeric material represented by the general formula (I) [In the formula, rings A and B may be substituted with a halogen atom, a lower alkyl group, an alkoxy group, or a phenyl group. X is a halogen atom or a phenylsulfonyl group; and a phenylene or naphthylene group in which two optionally substituted carbonyl groups are bonded at the ortho or peri position. Rings Y and Z may be substituted with halogen atoms. ] A method for coloring a polymeric material, characterized by coloring using a compound represented by the following.