JPS5812904B2 - 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 object of the present invention is to provide films, sheets, and
The purpose is to color molded products such as pipes and fibers in a yellow tone with excellent fastness, and it is based on the general formula [■] [wherein rings A and B are substituted with a halogen atom, a lower alkyl group, an alkoxy group, or a phenylene group]. You can leave it there.

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; however, in the present invention, the structural formula represented by the general formula [■] includes all of these general formulas [■a] [■] [Ib] including.

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

That is, the following general formula [■] or [where X may be substituted with a non-ionizable substituent,
A phenylene group or naphthylene group in which two carboxyl groups (carbonyl groups) are bonded at the ortho or peri position] Dicarboxylic acids or their dicarboxylic acid anhydrides represented by the following general formula [■] [wherein, ring A, B may be substituted with a halogen atom, an alkyl group, a phenyl group, or an alkoxy group.

Rings Y and Z may be substituted with halogen atoms] It can be produced by heating reaction with a quinoline derivative represented by the following.

Alternatively, without isolating the compound represented by the general formula [■], for example, 8-aminoquinaldine and the following formula [■] or [in the formula, Y and Z may be substituted with a halogen atom] can be used. It can be produced by reacting 2,3-naphthalene dicarboxylic acids or its dicarboxylic acid anhydrides under heating, then adding dicarboxylic acids represented by the general formula [■] or their acid anhydrides and causing a heating reaction. can.

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.

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, at least one of the naphthalene rings consisting of the phenylene group represented by X in the general formula [■], the naphthylene group, and the rings Y and Z contains a halogen atom. Those containing halogen atoms are preferred, and more preferably those containing halogen atoms are most 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, polyester, etc.

Also, paints, printing inks, etc. containing the above-mentioned polymeric materials can of course be colored by the method of the present invention.

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

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

Next, examples will be shown.

In the examples, "parts" 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 23
Mixing and extrusion at 0°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-(2,3-naphthalene dicarboimino)-quinaldine, 286 parts of tetrachlorophthalic 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 separated and 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 shown below and almost agreed with the calculated values.

Further, 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 above.

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 1 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.

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 from 155 to
The mixture was kneaded at 160°C to obtain a yellow sheet with excellent migration resistance, heat resistance, and light resistance.

Example 5 0.6 parts of the quinophthalone pigment represented by (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. A pellet was obtained.

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 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 this colored syrup was poured into a glass cell and heated at 50 to 70°C for 6 hours. After polymerization 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 polystyrene were mixed in a ball mill, and 300 parts of glass fiber, 240 parts of isophthalic acid type 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 One part of a quinophthalone compound having the following structural formula was uniformly dispersed in 3,000 parts of water containing 3 parts of sodium higher alkylbenzenesulfonate, 4 parts of O-phenylphenol was added, and 100 parts of polyester fiber was added to the dye bath. Soak 10 parts
Staining was carried out at 0-120°C for 2 hours.

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)

[Claims] 1. A polymeric material represented by the general formula [■] [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 phenylene group or a naphthylene group in which two carbonyl groups optionally substituted with a halogen atom or a phenylsulfonyl group 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.