JPS5813578B2 - 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 objective is to color molded products such as pipes, pellets, and fibers in a yellow tone with excellent fastness, and this is achieved by the general formula (1) [wherein rings A and B are a halogen atom, a lower alkyl group, an alkoxy group, or a phenyl group]. May be replaced.

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

Ring Y1Z 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 have a tautomeric structure as shown in the following formula, but in the present invention, the structural formula represented by the general formula CI This includes:

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

That is, the following general formula [■] [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 ortho or peri position.

Dicarboxylic acids or dicarboxylic acid anhydrides represented by the following 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.

Rings Y and Z 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 (m), for example, 8-aminoquinaldine can be converted to the following general formula (IV).
[In the formula, rings Y and Z may be substituted with a norogen atom.

It can be produced by reacting with diphenic acids represented by the formula (ID) or its acid anhydride under heating, and then adding dicarboxylic acids represented by the general formula (ID) or its acid anhydride.

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.

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 the general formula (I) are preferred.

Polymer materials to be colored in the coloring method of the present invention include polyolefins, polystyrenes, polyacrylonitrile, polyacrylates, polyvinyl chloride, polyacetals, polyamides, polycarbonates, amine resins, and acetic acid. Examples include cellulose type, epoxy resin type, and polyester type.

Furthermore, paints, printing inks, etc. containing the above-mentioned polymeric materials are of course colored using the coloring agent 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, etc., and/or heated and kneaded, followed by compression molding, injection molding, calendar molding, or extrusion molding. It is possible to color molded products such as films, sheets, fibers, pipes, pellets, etc. using ordinary molding methods such as molding methods.

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

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

Next, examples will be shown.

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

Example 1 0.24 parts of quinophthalone pigment represented by the following structural formula was blended with 200 parts of polystyrene resin, and 2 parts were mixed by a melt extruder.
By mixing and extruding at 30° C., a yellow colored Beresoto was obtained.

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 the blue scale rating was grade 6 or above.

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

364 parts of 8-(diphenimino)-quinaldine, 286 parts of tetraphthalic 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.

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, 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 and melt-extruded at 260 to 265°C to obtain a yellow colored beresoto.

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 a yellow colored Beresoto.

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 judged to be grade 6 or higher by blue scale.

Example 4 Two parts of a quinophthalone pigment represented by the following structure 2 and G (
After mixing 300 parts of 2-ethylhexyl phthalate with 700 parts of polyvinyl chloride resin, 155-
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 the formula (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. Colored beresotho 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 was observed depending on the injection conditions, 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. Then 3 at 100-120℃
After polymerization for a period of time, the resin 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 sil, and 300 parts of glass fiber were mixed with the mixture. 240 parts of isophthalic acid type unsaturated polyester resin, 1 part of calcium hydroxide
0 parts 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 sodium alkylbenzene sulfonate, 4 parts of 0-phenylphenol was added, and 100 parts of polyester fiber was added to the dye bath. was immersed and dyed at 100°C to 120°C for 2 hours.

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

Similarly, polyester fibers were 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 of the general formula [I] The rings A and B in the formula C may be substituted with a halogen 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 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.