JPS591300B2 - Coloring method for polymer materials - Google Patents

Description

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

More specifically, the present invention relates to a method of coloring a polymer material into a yellow tone with excellent fastness by using a specific compound. In this method, a polymer material containing the general formula [I] 0=CN/C=0 ~♀]・<:Crab[l] [However, X and z are chlorine atoms and/or bromine atoms, Y
represents a phenylene group or a naphthylene group in which two carbonyl groups are bonded at the ortho or peri position (these groups may be substituted with a nonionizable substituent such as a halogen atom), respectively. This is achieved by coloring with a compound that

The compound represented by the above general formula [I] used in the present invention has a tautomeric structure as shown in the following formula (wherein X.Z and Y are the same as those in the above general formula [1]). However, in the present invention, the general formula [1]
Compounds having the structural formula represented by the formula [1. Ia. Ib].

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

That is, halogenated phthalic acid or halogenated phthalic anhydride represented by the following formula [] (where z represents a chlorine atom or a bromine atom) is represented by the following formula [], in which x and Y are represented by the above general formula. It can be produced by heating and reacting with a quinoline derivative represented by the same meaning as in .

In addition, to isolate the compound represented by the above formula [], for example, a 2-methyl-8-halogen derivative represented by the following formula [] (wherein X is the same as above) and the following formula [] or ) [However, Y in the formula is the same as above] After reacting the dicarboxylic acids represented by the following or its dicarboxylic acid anhydride under heating, the phthalic acid derivative represented by the general formula [] or its acid anhydride derivative? It can also be produced by adding a substance and reacting it.

In the method of the present invention, any compound produced by any method can be used as long as it has a structural formula represented by the above general formula [1] or the like. Among the compounds used in the coloring method of the present invention, the following are preferably mentioned.

In the present invention, in addition to using the compound represented by the above general formula [1], further effects can be obtained by using an antioxidant, an ultraviolet inhibitor, etc. in combination.

Examples of the polymeric materials used in the present invention include polyolefins, polystyrenes, polyacrylonitrile, polyacrylates, polycarbonates, amino resins, cellulose acetate, epoxy resins, polyamides, polyesters, and other acrylonitriles. Materials such as -butadiene-styrene copolymer can be mentioned.

In carrying out the present invention, coloring can be achieved by blending a required amount of the compound represented by the general formula [1] into a polymeric material.

For example, a polymeric material containing a compound represented by the general formula [1] is heated and kneaded, and then processed into films, sheets, fibers, pipes by ordinary molding methods such as compression molding, injection molding, calendar molding, and extrusion molding. , molded products such as pellets can be colored yellow. Coloring can also be done by a cast molding method in which a compound represented by the general formula [1] is blended into a liquid monomer or prepolymer and polymerized and cured.As a colorant for paints, so-called paints, paints, and baking paints can be used. Coloring can also be achieved by blending the compound represented by the general formula [1] into a powder coating or an aqueous emulsion coating. It can also be used as a coloring agent in printing inks. Furthermore, fibers and textiles can be colored using the compound represented by the general formula [1] by a known dyeing method. The polymeric material colored by the coloring method of the present invention exhibits excellent heat resistance, light resistance, migration resistance, solvent resistance, clear coloring properties, and has an extremely excellent coloring effect.

Next, examples will be shown. Note that parts in the examples indicate parts by weight. Example 1 Quinophthalone pigment 2 represented by the following structural formula (1-1)
and 300 parts of di-(2-ethylhexyl)-phthalate were mixed with 700 parts of polyvinyl chloride resin, and then kneaded with a diroll at 155 to 160°C. The yellow sheet obtained was sandwiched between white PVC sheets, and 24 hours at ℃, 1k
A pressure of 77 liters of 9/C was applied.

No color transfer to the white PVC sheet was observed. In addition,
For comparison, when a KinoJalon pigment represented by the following structural formula (1-2) was treated in the same manner, color transfer to the PVC sheet was observed.
It has been found that the quinotaphthalone pigment represented by 1) exhibits excellent migration resistance.

Example 2 0.3 part of the quinophthalone pigment represented by the formula (1-1) shown in Example 1 was blended with 200 parts of polystyrene resin.
The mixture was mixed and extruded using a melt extruder at 30°C to obtain pellets colored yellow.

This pellet was injection molded under the following conditions 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 higher. The quinophthalone pigment used in this example was manufactured as follows.

172 parts of 2-methyl-5-amino-8-chloroquinoline, 572 parts of tetrachlorophthalic anhydride, 80 parts of zinc chloride
100 parts of dimethylformamide and 4000 parts of trichlorobenzene were reacted at the boiling point under reflux for 3 hours, and then 100 parts of dimethylformamide
0 part was added and stirred under reflux for 1 hour.

After cooling, P was removed and the yellow reaction product was washed with 2000 parts of dimethylformamide and finally with ethanol.
After drying, a yellow pigment with a melting point of 360° C. or higher and a maximum absorption in the visible spectrum of dimethylformamide around 428 mμ was obtained. The results of elemental analysis of this material were as shown below, which almost agreed with the calculated values. In addition, the following structural formula (A
), (B) and (C) were used to color polystyrene resin in the same manner as above, and similar results were obtained.

Example 3 Quinophthalone pigment 3 represented by the following structural formula was blended with 2000 parts of polycarbonate resin, and 260-265-C
The pellets were melt-extruded to obtain 40 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 4 1 part of quinophthalone pigment represented by the following structural formula and 5 parts of methyl-type titanium oxide were blended with 1000 parts of ABS resin,
The mixture was 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 yellow colored molded plate. 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 the blue scale evaluation was grade 6 or higher. Example 5 Two parts of quinophthalone pigment represented by the following structural formula and one part of di(
After mixing 300 parts of 2-ethylhexyl)-phthalate with 700 parts of polyvinyl chloride resin,
The mixture was kneaded at 55 to 160°C to obtain a yellow sheet with excellent migration resistance, heat resistance, and light resistance.

Example 6 0.6 parts of a quinophthalone pigment represented by the following structural formula and 3 parts of rutile titanium oxide were blended with 600 parts of a polypropylene resin, and mixed and extruded using an extruder to obtain pellets colored yellow.

This pellet was injection molded under the conditions shown in Table 4 to obtain a molded plate colored bright yellow. At this time, no change in color tone was observed depending on the injection conditions, and excellent heat resistance was exhibited.
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 syrup, and this colored syrup was poured into a glass cell and heated at 50 to 70°C for 6 hours. Then, after polymerizing at 100 to 120° C. for 3 hours, it was cooled and peeled off to obtain a robust yellow polymethyl methacrylate resin plate.

Example 8 1 part of the quinophthalone pigment represented by formula (1-1) used in Example 1, 386 parts of calcium carbonate, 4 parts of zinc stearate, 25 parts of styrene monomer, 3 parts of finely powdered polystyrene
5 parts were mixed in a ball mill, 300 parts of glass fiber, 240 parts of isophthalic acid type unsaturated polyester, and 10 parts of calcium hydroxide were mixed, and a polymerization initiator was added to make 180 parts.
When heated and molded at ℃, a reinforced polyester molded product with a bright yellow color was obtained.

Example 9 18 parts of the quinophthalone pigment represented by the formula (1-1) used in Example 1 and 282 parts of commercially available clear (melamine-alkyd paint) were milled in a pot mill for 40 hours, taken out from the pot, diluted with thinner, and made into a tin plate. The plate was spray-painted, left to stand for 15 minutes, and then baked at 130°C for 30 minutes to obtain a bright yellow coated plate.

Example 10 1 part of the pigment represented by the following structural formula was uniformly dispersed in 3,000 parts of water containing 3 parts of higher alkylbenzene sulfonic acid sodium, 4 parts of O-phenylphenol was added, and in this dye bath 100 parts of polyester fiber is immersed in 100~
Staining was carried out at 120°C for 2 hours.

Claims (1)

[Claims] 1 A polymeric material is defined by the general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [However, X
and Z is a chlorine atom and/or a bromine atom, and Y is a phenylene group or naphthylene group in which two carbonyl groups are bonded at the ortho or peri position (these groups may be substituted with a halogen atom) ) respectively. ] A method for coloring a polymer material, the method comprising coloring a polymer material using a compound represented by the following.