JPS58118856A - Isoindolinone compound and method for coloring high-molecular organic material by using the same - Google Patents

Abstract

PURPOSE:To produce a yellow molding which exhibits less shrinkage anisotropy and has excellent dimensional stability as well as excellent resistance to heat, chemicals and light, by coloring and molding by meeting a high-molecular org. material by using a specified isoindolinone compd. CONSTITUTION:A high-molecular org. material such as PE is colored yellow and molded by melting by using an isoindolinone compd. of formulaI, wherein X is Cl, Br. Heretofore, it has been known that the addition of a pigment to polyolefins has a deleterious effect on dimensional stability. Particularly, PE is easily crystallized during molding, so that there is a tendency that moldings shrink, the finish size is shortened, the degree of shrinkage varies depending on the flow direction of a molten resin, and distortion or strain takes place. When the known compd. of formula II is used, dimensional stability is very poor, so that the use thereof is limited. By using the compd. of formulaI, colored moldings having excellent dimensional stability and resistance can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an isoindolinone compound and a method for coloring the same.

More specifically, it is a yellow formula (in the formula, X represents chlorine or bromine) that does not cause deformation such as recoil distortion of the molded product due to crystallization and shrinkage of polyethylene, etc. during melt color molding of polyethylene, etc. This invention relates to the isoindolinone compound shown and a method for coloring polymeric organic materials using the same.

Conventionally, polyolefins have been used in a wide variety of fields as general-purpose synthetic resins, and in many cases, they are given various colors with pigment colorants, increasing their commercial value, but the addition of pigments impedes dimensional stability. It is known. In particular, polyethylene and resins tend to crystallize during molding, which not only causes shrinkage in the molded product and reduces the finished dimensions, but also causes shrinkage to vary depending on the direction of the flow of the molten resin (shrinkage anisotropy). ), causing distortion and distortion. Such a phenomenon may be noticeable when an organic pigment is used as a coloring agent.

The cause of such shrinkage anisotropy when using organic pigments has not yet been elucidated, but the degree of shrinkage anisotropy, that is, the dimensional stability, depends on the structure of the organic pigment. It is known that there are significant differences. In addition, several methods have been proposed for improving the dimensional stability of resin molded products using organic pigments from the viewpoint of organic pigments.

That is, (-1) A method of coating the pigment surface with another substance.

For example, melamine formaldehyde thermosetting resin,
A method of surface-treating pigments by adding a modifier such as organic silane or organic titanate (Japanese Patent Laid-Open No. 50-44247,
Japanese Patent Application Publication 1973-. No. 101440, JP-A-61-Ma353
No. 0, Japanese Unexamined Patent Publication No. 5, No. 74039).

(2) A method of changing the crystal form of pigments.

A method of changing the effect on shrinkage by changing the properties of the surface being coated (JP-A-50-134042, JP-A-51-
No. 22'744, JP-A-51-81653, JP-A-5
(No. 6-99245) (3) A method of changing the properties of the pigment surface.

For example, a method of introducing substituents into an organic pigment with a certain structure to create a pigment with a similar structure and changing the surface properties (Japanese Unexamined Patent Publication No. 50/1983)
(No. 18551, Japanese Unexamined Patent Publication No. 11136/1983) These methods have advantages and disadvantages. For example, in method (1), the modifier used must have no adverse effect on light resistance, heat resistance, etc. From this point of view, treatment with inorganic substances is preferable, but coating organic pigments with inorganic substances is , is technically extremely difficult.

Method (2) is a method to improve the shrinkage anisotropy by controlling the crystal size, but at present, pigments that are known to improve shrinkage by this method The number is small. (This method often impairs the color tone and color resistance of the original pigment, which has a different structure from the original pigment.

It is well known that this compound is useful as a greenish yellow pigment with excellent heat resistance, light resistance, chemical resistance, etc., and is used in the paint field.
Widely used. However, this pigment has very poor dimensional stability when coloring polyolefin resin, which is a drawback of organic pigments, and its uses have been limited.

As a result of intensive research on the dimensional stability of colored molded products of polyolefin resins containing inindolinone pigments, the present inventors found that the isoindolinone compound of formula (1) has a shrinkage characteristic of colored polyolefin resins. It has been found that the dimensional stability is significantly improved without causing any tropism.

The compound of formula (1) can be produced as follows.

The first method is to add 1 mole of 2.6-Siamitutoluev to the 3
4.5.6. with two methoxy groups or two chlorine atoms in the - position. +7-chitrapromoisoindoline
This method involves condensation with 2 moles of -1-one. The second method is to combine 1 mole of 2.6-reamitsutoluev with 4.5.6 with two methoxy groups or two chlorine atoms in the 3-position.
．． This is a method in which the compound is condensed with 1 mole of 7-teto-2-proisoindoline-neion, and then condensed with 1 mole of 1 and 1 of the 7-teto-2-promoisoindoline-neone.

4, 5.6. '/-tetrab47 (or tetrachloro)-isoindolin-1-one can be prepared by adding a chlorinating agent such as phosphorus pentachloride to tetrabromophthalimide or nat2
By reacting with chlorophthalyl heptaide, Part 3
A compound having two chlorine atoms at the - position is obtained.

3,3-Dichloro Ichiban S made in this way 5$ 61
7-tet 2b pmoisoindolin-1-one or 3
, 3.4.5.6. '7-hexac4roinindolin-1-one was converted into 3,3-
Dimethoxy-4,5,6,'/-tetrappmoisoindolin-1-one or 3,3-dimethoxy-4,5,6
Kufutetrachloroisoindoline can be changed to 1 to 1 to 1 to 1.

On the other hand, 3.4.5. f3-tetrabromo-2-cyanobenzoic acid or 3.4.5.6-titrachlorou-2-cyanobenzoic acid, each ester, for example, the methyl ester, in the presence of alkali gold X or alkaline earth metal, 4.5.6. has two methoxy groups at the 3-position by reacting with methanol. Tutetrapromoin indolin-1-one or 4.5.6. γ-tetrachloroisoindolin-1-one can also be made.

4.5.6. having two chlorine atoms or 2@methoxy groups at the 5-position with the 2,6-diagunotoluene; '/-
Tetrabromoine indolin-1-one or 4,5.
13. The condensation reaction with '7-titrachloroisoindolin-1-one takes place in the cold, but in some cases it may be carried out by heating the homogeneously mixed reaction components to, for example, 50 to 200°C. can.

Note that it is advantageous to carry out the condensation in the presence of an inert organic solvent, such as benzene, toluene, xylene monochlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene, etc., that is, an organic solvent that does not take part in the reaction.

As a raw material, 3.4,5.6-tetrapromo 2-cyanobenzoic acid methyl ester or 3.4.5.6-teto2
When using chloro-a-2-cyanobenzoic acid methyl ester, 5,3-dimethoxy-4,5,6,tutetrabromo-isoindolin-1-one or 3,3-dimethoxy-4,5, It is obtained as a metal salt of 6,2-tetrachloro-isoindolin-1-one, and the metal salt, especially the sodium salt, is condensed with 2,6-diamittoluene and then hydrolyzed with an organic acid such as acetic acid. Alternatively, a sodium salt of metal #11F# before condensation may be hydrolyzed with an organic acid and then condensed with 2,6-diamittoluene.

In the second method, for example, 1,1-dimethoxy-
2 mol of a mixture of 4,5,6,7-titraptetramoisoindolin-3-one and 1,1-dimethoxy-4,5,6,'7-titraptetramoisoindolin-3-one and 2,6
- When 1 mole of diammetluef is condensed with and K, the formula C
It is also possible to prepare mixtures of compounds of formula I) and of formula CI).

The polymeric organic material to be colored with the compound of formula (13) of the present invention is a polyolefin synthetic resin such as polyvinyl chloride, polyethylene, polypropylene, polystyrene, a copolymer thereof, or a blend containing them. However, among polyolefin resins, polyethylene, especially medium and low pressure polyethylene, has remarkable deformability, and polyethylene is an important target in the present invention.

The main method for applying the isoindolinone compound of the formula CD of the present invention is the melt cross-coloring method, and the molding methods include, for example, injection molding, extrusion molding, blow molding, vacuum molding, and the like. These methods are already well known. An uncolored polyolefin resin and the above-mentioned isoindolinone compound are melt-kneaded and molded immediately, or once formed into pellets, etc., and then either as is or with the addition of an uncolored resin, melted and molded to produce a colored molded product. is obtained. There is no particular limit to the amount of the formula CD inindolinone compound added to the resin, but it is usually 0.
A value of 0.05 to 0.6 is sufficient, and it can be changed arbitrarily according to the requirements for filtration and coloring density of the final product.

By using the compound of formula [1] of the present invention, a molded product with small shrinkage anisotropy, excellent dimensional stability, and excellent heat resistance, chemical resistance, and light resistance can be obtained.

In addition, compounds of formula [r] and ([3) manufactured in such a way that they form a mixture during production also have extremely poor dimensional stability.
Even in the case where the compounds 1) and (II) are produced individually and then mixed together, the dimensional stability becomes better as the ratio of formula (1) increases.

Generally speaking, the compound of formula (1) is a polyolefin such as polyethylene or polypropylene, or ethylene or propylene and vinyl chloride, vinyl acetate or acrylonitrile #P
It has also been found that coloring the polyolefin resin obtained by copolymerizing , ) does not impair dimensional stability.

The present invention will be explained below with reference to examples.

In the examples, all ``chi'' and ``parts'' indicate weight % and parts by weight.

Example 1 1. Add 3,4,5,6 to 200 parts of 2-dichlorobenzene.
- Tetraptera mo 2-cyanobenzoic acid methyl ester (
A sodium methylate solution (obtained from 0.1 part of sodium and 25 parts of methanol) was added to a solution of 14.6 parts of 122°C) at 25-35°C.
After stirring for 0 minutes, 1,1-dimethoxy-4,5,6,'
The sodium salt of 7-titrabromoisoindolin-3-one is obtained. When 6.5 parts of glacial acetic acid is added to this solution, 1
, 1-dimethoxy-4,5,6,tutetrabromoisoindolin-3-one is obtained.

Add 83 parts of 2,6-diamitluent to this solution,
Heat to raise temperature. At the same time as methanol is distilled from around 0°C, bis(4,5,6;2-tetrabromoisoindolin-3-one-1-ylidene-1-methylphenylenediamine (2,6) is produced and precipitated.100 The temperature was raised to 0.degree. C., stirred for 60 minutes at the same temperature to complete the reaction, and the temperature was further raised to obtain 13.4 parts of compound 140 (compound of formula (I) in which X is bromo).

X-ray diffraction measurement (2θ) results: Relatively strong diffraction intensities at 5.6° and 311°; 22·′y
Moderate diffraction intensity at 0°252° and 295°; 12・Q
6119.3', 2 B, 00. Weak diffraction intensity at 33.00 and 35.20.

Example 2 3.4,5.6- to 300 parts of 1,2-dichlorobenzene
Tetrachloro-2-cyano-benzoic acid methyl ester (
m, p, 84°C) 9.15 parts and 3.4.5.6-tetrapromo 2-cyano-benzoic acid methyl ester 14.
6 parts of sodium methylate solution (obtained from 1.4 parts of sodium and 50 parts of methanol)
When added and stirred at 25-35°C for 30 minutes, 1. Sodium salt of l-dimethoxy-4,5,6,tutetrachloroisoindolin-3-one and 1,1-dimethoxy-
The sodium salt of 4,5,6,tutetrabromoisoindolin-3-one is obtained.

3.66 parts of 2,6-diamitluene is added to this solution and heated. From around 10°C, methanol is distilled off and N'a salt of the pigment is formed and precipitated. Raise the temperature to 00'C,
The reaction mixture is stirred at the same temperature for 60 minutes to complete the reaction, and then 8.6 parts of glacial acetic acid is added dropwise to the reaction mixture to make it acidic, and the mixture is further heated and stirred at 140 to 150°C for 120 minutes. The produced insoluble pigment is separated in a hot furnace, washed with methanol and water, and dried. 23.4 parts of a green-yellow compound C (mixture of a compound of the formula CI) in which X is chloro, a compound in which X is bromo and a compound of the formula (II)) are obtained.

X-ray diffraction measurement (2θ) results Relatively strong diffraction intensity at windows 5.8°, 25.6°, and 31.0° 123.1°, moderate diffraction intensity at 29.0°; 11
・4°.

Weak diffraction intensity at 19.5° and 21.0°.

Example 3 3.4, 15.6 to 250 parts of 1.2-dichlorobenzene
-tetrabromo-2-cyanobenzoic acid methyl ester 1
Add sodium methylate solution (
(obtained from sodium 0.maf and 40 parts of methanol) and stirred at 25-30°C for 30 minutes.
The sodium salt of 1-dimethoxy-4,5,6, futetrapromoisoi nodlin-3-one is obtained. To this solution (4,5,6,7-titrachloroisointolin-1
When 11.6'7 parts of -one-3-ylene)-2'-methyl-phenylenediamine-(1/, 3/) is added and heated, it becomes a solution and at the same time methanol is distilled off, the pigment Na Salt is produced.

The temperature is raised to 100°C, stirred at the same temperature for 60 minutes to complete the reaction, 4.3 parts of glacial acetic acid is added dropwise to the reaction mixture to make it acidic, and the mixture is further heated and stirred at 140 to 150°C for 120 minutes. . The generated insoluble pigment was separated by heat separation, and methanol,
Wash with water and dry. 21.8 parts of a green-yellow compound (compound in which X is chloro in formula (I)) is obtained.

X-ray diffraction measurement (2θ) result f Relatively strong diffraction intensity at 5.7° and 31.1° i25.8
°.

Relatively strong diffraction intensity i 1 at 29.1° and 29.4°
1.50°11.20. 23.00. Weak diffraction intensity at 34.8'.

Usage example 1 High-density polyethylene (Mitsui Petrochemicals, Hi-Zex 2)
200J) was used as the resin to be colored, and Example 1 was applied to this.
, 0.1% of the compound obtained in step 2.3 and 1% of dispersant (metallic soap) were added to each, and the mixture was blended using a blender. line) K, and the deformability of the molded products made from the above compound was determined and compared.

The molding conditions are injection temperature 220℃, injection pressure 22b Gs
The injection time was 6 seconds, the mold temperature was 55° C., and cooling was 20 seconds, and the molded product was left for one day after being taken out.

Two types of molds were used: a rectangular flat plate and a disc-shaped mold.

The mold for the rectangular flat plate is 100 mm vertically, 70 mm horizontally, and 2 mm thick.
The flow direction of the molten resin is the vertical direction.

The shrinkage of the obtained rectangular flat plate molded product is expressed by the shrinkage percentage shown below.

The disk-shaped mold has a diameter of 100 mm and a thickness of 2 mm, and the molten resin is injected from the center of the disk.

Place the obtained disc-shaped molded product on a flat surface and check the warpage of the disc (
) was defined as the degree of deformation.

The results are shown in Table 1.

From this result, the compounds obtained in each of Examples 1 and 2.3 showed shrinkage rates and deformation degrees close to those of the blank test,
It can be seen that a molded product with excellent dimensional stability can be obtained.

Comparative Example U 0.1% of the compound represented by the structural formula (ff) and 0.1% of the dispersant (metal soap) were added to the same high-density polyethylene as used in Use Example 1, and the same as used in Use Example 1 was added. The shrinkage rate and degree of deformation were measured based on the dimensions.

The results are shown in Table 1.

As seen in the results, the compound represented by the structural formula
It shows considerably less dimensional stability than the compounds of the invention.

Use Example 2 A mixture obtained by mixing the compound obtained in Example 1 and the compound represented by Structural Formula (II) in the same high-density polyethylene as used in Use Example 1 at a ratio of 1+1.0.1 % and 0.1 g of a dispersant (metallic soap) were added, and the shrinkage rate and degree of deformation were measured in the same manner as in Use Example 1.

The results are shown in Table 1.

As seen in the results, this mixture exhibits a shrinkage rate and degree of deformation close to those of the blank test, and it is understood that a molded product with excellent dimensional stability can be obtained.

Table 1

Claims (1)

[Scope of Claims] An isoindolinone compound represented by the formula (wherein X represents chlorine or bromine). A method for coloring a polymeric organic material, characterized by using an inindolinone compound represented by the formula (wherein X represents chlorine or bromine).