JPS6237053B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a coloring agent for polyolefins containing a novel isoindolinone pigment that does not cause deformation due to shrinkage in molded products during melt color molding of polyolefins, particularly polyethylene. Traditionally, highly toxic heavy metal pigments such as cadmium-based, chromium-based, and lead-based pigments have been used to color polyolefins, but from the perspective of pollution prevention, the use of these heavy metal pigments has been regulated and refrained from being used, and organic pigments have been replaced. It became necessary to hire. As a yellow organic pigment to replace the heavy metal pigment, the general formula (In the formula, X' is a chlorine atom or a bromine atom, R' is an aromatic group or a heterocyclic group, and n is an integer of 0 or 1 to 4.) Pigments have excellent heat resistance, weather resistance, and migration resistance, but when polyolefins, especially polyethylene, colored with these pigments are melt-molded, the molded product may suffer from distortion, warping, etc. due to shrinkage. This has been a major obstacle in practical use. Generally, when the molten polyolefin is cooled, the organic pigment particles act as crystal nuclei, which promotes crystallization of the resin, resulting in uneven shrinkage, resulting in deformation such as distortion and warping of the molded product as a whole. is thought to occur. The present inventors investigated the correlation between the shape of pigment particles and distortion, warping, etc. of molded products, and found that needle-shaped pigment particles generally tend to cause deformation of molded products, while spherical or granular pigment particles tend to cause deformation of molded products. It has been found that the general case is less likely to cause deformation. This fact is due to the fact that during melt molding of polyolefin, needle-like crystals are oriented in the flow direction of the resin in the resin matrix, and as a result, the molding shrinkage in the flow direction is larger than the molding shrinkage in the perpendicular direction, resulting in an imbalance of shrinkage. It is presumed that this causes deformation of the molded product. Isoindolinone pigments that are currently commercially available and which cause deformation in molded articles all have columnar or needle-like crystals. As a result of various studies based on the above findings, the present inventors have discovered that salts of isoindolinone dyes and bases,
Isoindolinone pigments, which are obtained by dispersing the pigment in water, adding an organic solvent that is not freely miscible with water, and hydrolyzing it in a conventional manner, have a spherical or granular particle shape and a uniform particle size. Therefore, the pigment does not cause deformation of the molded product, and furthermore, the pigment has a clear hue, extremely high hiding power, excellent dispersibility, coloring power, etc., and is also commercially superior in weather resistance, light resistance, and heat resistance. It was discovered that this pigment is significantly improved compared to isoindolinone pigments, and the present invention was completed. That is, the present invention provides an isoindolinone dye represented by the following general formula (). (In the formula, X represents a chlorine atom or a bromine atom, R represents an aromatic group or a heterocyclic group, and n represents an integer of 0 or 1 to 4, respectively.) After dispersing the salt of and a base in water, The present invention relates to a coloring agent for polyolefin containing an isoindolinone pigment obtained by adding an organic solvent that is not freely miscible with water and causing hydrolysis. In the present invention, the isoindolinone dye used as a starting material may be either a crude pigment before pigmentation treatment or one subjected to pigmentation treatment by a conventional method. The isoindolinone dye represented by the above general formula () is already known from US Pat. No. 2,573,352, Japanese Patent Publication No. 34-4488, and other documents, Representative examples of heterocyclic groups include 1,2
-, 1,3- or 1,4-phenylene group, 2,
2'- or 4,4'-diphenylene group, 4,4'-diphenylene sulfide group, 4,4'-diphenylene urea group, stilbene-4,4'-ylene group, benzoylaniline-4,4' -Ylene group, azobenzene-
4,4'-ylene group, 4,4'-diphenylene ether group, 4,4'-diphenylenemethane group, 1,4-
Aromatic groups such as naphthylene groups, pyridine-2,6-
or -2,5-ylene group, carbazole-3,6
Examples include heterocyclic groups such as -ylene group. Of course, these groups may have a substituent such as a lower alkyl group, a lower alkoxy group, or a halogen atom. Examples of bases that can form salts with isoindolinone dyes include those described in Japanese Patent Publication No. 39565/1983 and Japanese Patent Application Laid-Open No. 1983-1989.
25526, etc., for example, alkali metal hydroxides, carbonates, alcoholates, amides, etc. and alkaline earth metal hydroxides,
Examples include inorganic bases such as oxides, amines such as monoalkylamines and dialkylamines, and organic bases such as quaternary ammonium hydroxide compounds such as benzyltrimethylammonium hydroxide. In addition, the formation of a salt between the above dye and a base is as follows:
Each can be reacted in water in the presence or absence of other solvents, and can often be confirmed by a change in color after the reaction. The hydrolysis reaction of the salt, which is carried out by adding an organic solvent that is not freely miscible with water after decomposition into water, is a rapid reaction that proceeds easily even at room temperature. The hydrolysis temperature has a large effect on the diameter of the pigment particles produced; the higher the temperature, the larger the particle diameter, the smaller the specific surface area of the particles, and the higher the hiding power. Therefore, the hydrolysis temperature generally ranges from 0 to
100℃, using autoclave if necessary
Although the temperature may be set at 100°C or higher, the pigment treatment intended for the purpose of the present invention can usually be carried out sufficiently at a temperature in the range of 20 to 90°C.
Although the hydrolysis time depends on the temperature setting conditions, it usually takes less than one hour, and depending on the conditions, it may take more than one hour. Organic solvents that are not freely miscible with water include, for example, benzene, toluene, xylene, ethylbenzene and other (poly)alkylbenzenes, nitrobenzene, mono-, di- or tri-chlorobenzene, anisole, phenethole, dimethylaniline, quinoline, decalin, di- - or trichloroethane, n-hexane, cyclohexane, saturated aliphatic alcohol having 4 to 8 carbon atoms, benzoic acid methyl ester, benzoic acid ethyl ester, dipropyl ether, dibutyl ether, dioxane, tetrahydrofuran, liquid paraffin, diphenyl, Aromatic and aliphatic compounds such as diphenyl ether, zaphenylmethane, phthalate esters, and derivatives thereof are included. The ratio of the organic solvent to water is preferably 0.05 parts or more per 100 parts by weight of water (hereinafter simply referred to as "parts"), and is preferably 10 parts or less considering the step of washing the pigment particles after hydrolysis. . The colorant for polyolefins according to the present invention contains the novel isoindolinone pigment obtained as described above, and is used to improve the hue, physical strength, durability, etc. of molded products, and also to improve the coloring agent in the molding process. Due to the above requirements, other commonly used pigments,
It can be used in combination with extender pigments and various additives such as surfactants, plasticizers, dispersants, dispersion aids, excipients, antistatic agents, antioxidants, and ultraviolet absorbers. It can also be used by kneading it with a resin, low molecular weight polyethylene, polypropylene, etc. in advance. Therefore, the colorant according to the present invention is
It is used in various forms such as powder, granules, pellets, beads, flakes, and pastes. Examples of the polyolefin which is the resin to be colored include various grades of polyethylene, polypropylene, polystyrene, modified or copolymer resins thereof, and the coloring agent according to the present invention is particularly important for polyethylene. Next, an example of manufacturing the isoindolinone pigment used in the present invention will be given. Production Example 1 20 parts of sodium salt of bis-(4,5,6,7-tetrachloroisoindolin-1-one-3-ylidene)-phenylenediamine (1,4) was dissolved in water.
After dispersing in 200 parts, 20 parts of xylene was added, the temperature was raised, and the mixture was stirred at 80°C for 1 hour. The pigment generated by hydrolysis was transferred to the xylene layer and separated from the water. After separating and removing the colorless and transparent water layer, add 200 ml of water.
The mixture was stirred and heated, and xylene was distilled off azeotropically. The reddish yellow crystals were heated, thoroughly washed with water, and then dried to obtain 17 parts of a reddish yellow pigment. Production Example 2 25 parts of n-butylamine salt of bis-(4,5,6,7-tetrachloroisoindolin-1-one-3-ylidene)-1-methylphenylenediamine (2,6) was added to 300 parts of water. After dispersing in the mixture, 5 parts of quinoline was added, the temperature was raised, and the mixture was stirred at 60°C for 1 hour.
The bluish crystals were filtered, thoroughly washed with water, and then dried to obtain 18 parts of a bluish yellow pigment. The present invention will be described below with reference to Examples and Comparative Examples. The method for measuring the degree of deformation, shrinkage rate, and shrinkage ratio is as follows. (1) Degree of deformation Using a disc-shaped mold with a diameter of 120 mm and a thickness of 2 mm,
A disk is molded using a 3-ounce inline injection molding machine at a molding temperature of 220°C. This disk was heated to 48℃ at 25℃.
After leaving it for a while, one side of the disk placed on a flat surface is lightly held down, and the height from the flat surface at which the warp on the opposite side is maximum is defined as the degree of deformation. (2) Shrinkage rate and shrinkage ratio A flat plate with a length of 140 mm, width of 80 mm, and thickness of 2 mm is used to mold a flat plate at a molding temperature of 220°C using a 3-ounce in-line screw injection molding machine. After this flat plate was left at 25°C for 48 hours, the lengths in the vertical and horizontal directions were measured, the shrinkage rates in the vertical and horizontal directions were determined based on the following formula, and the shrinkage ratio, which was the ratio of these, was determined. Vertical shrinkage rate = Vertical mold dimension - Vertical molded product dimension / Vertical mold dimension The horizontal shrinkage rate is based on the above formula. Shrinkage ratio = longitudinal shrinkage ratio / transverse shrinkage ratio Example 1 A dry color was prepared from 1 part of the isoindolinone pigment obtained in Production Example 1 and 1 part of zinc stearate, and 2 g of the dry color and high density A dry blend of 1000 g of polyethylene (MI: 6, density 0.970 g/cm ³ ) was molded into disks and flat plates using the injection molding machine. Table 1 shows the results of measuring the degree of deformation, shrinkage rate, and shrinkage ratio of the molded product. Comparative Example 1 Instead of the pigment used in Example 1, isoindolinone yellow (IrgazinYellow3RLTN, Pig.
Yellow 110) were used to mold discs and flat plates in the same manner as in Example 1, and the degree of deformation of the molded products was measured. The results are shown in Table 1.

[Table] * Example 2 When non-colored products are molded in the same manner. Disks and flat plates are made in the same manner as in Example 1 using the isoindolinone pigment obtained in Production Example 2 instead of the pigment used in Example 1. was molded and the degree of deformation etc. was measured. The results are shown in Table 2. Comparative Example 2 Isoindolinone yellow (IrgazinYellow2GLT, Pig.Yellow109) having the same chemical structural formula as the pigment was used instead of the pigment used in Example 2.
Disks and flat plates were molded using the same method as in Example 2, and the degree of deformation of the molded products was measured. The results are shown in Table 2.

[Table] Examples 3 to 17 In place of the pigments used in Example 1, the pigments listed in Table 3, which were manufactured according to the method described in Production Example 1, were used, and a disk was prepared in the same manner as in Example 1. A flat plate was formed and the degree of deformation etc. was measured. The results are shown in Table 3. Comparative Examples 3 to 17 In place of the pigments used in Examples 3 to 17, Examples 3 to 17 were produced by the method described in Japanese Patent Publication No. 1983-4488, which is conventionally known as a method for producing isoindolinone pigments. Using a pigment having the same chemical structural formula as the pigment listed in (1), disks and flat plates were formed in the same manner as in the examples above, and the degree of deformation etc. was measured.
The results are shown in Table 3.

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Claims (1)

[Claims] 1. Isoindolinone dye represented by the following general formula (In the formula, X represents a chlorine atom or a bromine atom, R represents an aromatic group or a heterocyclic group, and n represents an integer of 0 or 1 to 4, respectively.) After dispersing the salt of and a base in water, A coloring agent for polyolefins containing an isoindolinone pigment obtained by adding an organic solvent that is not freely miscible with water and causing hydrolysis.