JPS598304B2 - Iminoisoindolinonganryyounoseizohouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the following formula (I) represents a hydrogen atom or a halogen atom, and substituents X_1 and X_
One of 4 represents a halogen atom, and the substituent X_2
and if at most one of X_3 represents a halogen atom, and X_0 represents a hydrogen atom, then X_3
must not be a chlorine atom, or X_2 represents a cyano group or a carboxylic acid ester group, and
The present invention relates to a method for producing a novel iminoisoisotrinon pigment represented by _4, X_3 and X_4 each representing a hydrogen atom.

Among the compounds represented by formula (1), particularly useful pigments are:
In the formula, substituents X1 to X4 represent a hydrogen atom or a chlorine atom, one of the substituents X and X4 represents a chlorine atom, and at most one of the substituents X2 and X3
When each represents a chlorine atom and X1 represents a hydrogen atom, there is a compound in which X3 cannot be a chlorine atom.

Particularly preferred pigments have the following formula (): (wherein X1 to X4 have the above meanings, and Y1 and Y2 represent a hydrogen atom, a chlorine atom, or an alkyl or alkoxy group having 1 to 4 carbon atoms. )
It is a compound represented by the formula, and a compound in which Y1 and Y2 represent a hydrogen atom is particularly preferred.

The manufacturing method of the present invention is based on the following formula (auto): [wherein X1 to X4 have the meanings in formula (I},
or ``1 (in the formula, Y4 represents an imino group and Y3 represents a halogen atom, an alkoxy group, or a tertiary amino group)] isointrinone represented by 2:1 By condensing with a diamine represented by the following formula (in the formula (1)) in a molar ratio, the following formula (1): (in the formula,
A1 and X1 to X4 have the above-mentioned meanings) is a method for obtaining a novel iminoisointrione pigment.

Among the starting materials represented by formula (11), in the formula, substituents X1 to X4 represent a hydrogen atom or a chlorine atom, one of the substituents X and X4 represents a chlorine atom, and the substituent X2 and when at most only one of X3 represents a halogen atom and X1 represents a hydrogen atom,
Isointrinones in which 3 represents a hydrogen atom are preferred.

The isointrinones used as starting materials contain, in position 2, one imino group, two halogen atoms, two tertiary amino groups, such as for example piperidino or morpholino groups, or in particular one or more 2 with 4 carbon atoms
alkoxy groups, preferably methoxy groups.

Preferred isointrinones are represented by the following formula (VI): (wherein X1 to X4 have the above meanings, and R is 1 to 4
an alkyl group, preferably a methyl group, having 5 carbon atoms.

3,3-dialkoxyisointrinones have the following formula (VI
): (In the formula, X1 to X4 represent the above meanings.)

-Cyano-benzoic acid alkyl esters are obtained by reacting with an alkali metal alcoholade solution in a lower alcohol. In principle, it is not necessary to separate the isointrinones obtained as described above. In many cases, it can be used directly to react with diamines. 3-Iminoisointrinon is the equivalent.

- Obtained by reacting an alkyl cyanobenzoic acid ester with ammonia. The o-cyanobenzoic acid ester represented by the formula (4) has the following formula n): (wherein, X
1 to X4 and R have the above-mentioned meanings) are sequentially subjected to a Sandmeyer reaction, a diazotization reaction, and then reacted with potassium cyanide.

The following are examples of suitable O-cyano-benzoic acid esters: for example 6-chloro-2-cyano-benzoic acid methyl ester, 4-chloro-2-cyano-benzoic acid methyl ester, 6-fluor-2-cyano-benzoic acid methyl ester, cyanomonobenzoic acid methyl ester, 5-iodo-2-cyano-benzoic acid methyl ester, 3,4-dichloro-2-cyano-benzoic acid methyl ester, 3,5-dichloro-2-cyano-benzoic acid methyl ester, 4,6-dichloro-2-cyano-benzoic acid methyl ester, 2,4-dicyano-benzoic acid methyl ester, 2-cyano-terephthalic acid dimethyl ester.

Diamines represented by formula (V) suitable for use in the reaction include benzene-based diamines, e.g. For example, p-phenylenediamine is preferred, and has the following formula: (wherein Y1 and Y
2 represents a hydrogen atom, a chlorine atom, or an alkyl or alkoxy group having 1 to 4 carbon atoms).

Particularly preferred is p-phenylenediamine.

Examples of suitable diamines include: 1,4
-diaminobenzene, 1,3-diaminobenzene, 1,
3-diamino-4-methylbenzene, 1,3-diamino-4-methoxybenzene, 1,3-diamino-2-methylbenzene, 1,3-diamino-2,5-dichlorobenzene, 1,4-diamino -2-chlorobenzene, 1,4
-diamino-2-bromobenzene, 1,4-diamino-
2,5-dichlorobenzene, 1,4-diamino-2-methylbenzene, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2-methoxybenzene, 1
, 4-diamino-2,5-dimethoxybenzene, 1,4
-diamino-2-chloro-5-methylbenzene, 1,4
-diamino-2-chloro-5-methoxybenzene, 1,
4-diamino-2-chloro-5-ethoxybenzene, 1
, 4-diamino-2,5-diethoxybenzene, 1,4
-diaminonaphthalene, 1,5-diaminonaphthalene.

The condensation reaction occurs particularly advantageously in the presence of an inert organic solvent, i.e. an organic solvent that does not take part during the reaction, although it takes place with partial cooling, if necessary by heating the well mixed reactants. .

3-imino-isoindolin-1-one, 3-thio-isoindolin-1-one or 3,3-bis-tertiary amino-isoindolin-1-one or 3,3-dialkoxyisoindolin-1-one When using an alkali metal salt of 1 as a starting material, for example lower aliphatic alcohols such as lower alkanols (e.g. methanol, isopropanol or butanol); lower cyclic ethers such as dioxane or ethylene glycol monomethyl ether; or acetone. It is advantageous to use water-miscible organic solvents such as lower aliphatic ketones.

In this case, the condensation reaction occurs even at relatively low temperatures. The abovementioned reactions are advantageously carried out in the presence of a base binder, such as, for example, lower fatty acids, especially acetic acid, which at the same time acts as a solvent. When using 3,3-dihalogenoisoindolin-1-one, the following organic solvents without hydroxyl groups are preferred in the presence of an acid binder.

i.e. hydrocarbons, e.g. aromatic hydrocarbons (e.g. benzene, toluene, xylene, tetrahydronaphthalene, diphenyl, etc.); cycloaliphatic hydrocarbons, e.g. cyclohexane; halogenated hydrocarbons, e.g. aliphatic halogenated hydrocarbons. (e.g. carbon tetrachloride, tetrachloroethylene, etc.), aromatic halogenated hydrocarbons (e.g. chlorobenzene, dichlorobenzene, trichlorobenzene, etc.); aromatic nitrogen monohydrocarbons, e.g. nitrobenzene; ethers, especially aliphatic ethers (e.g. dibutyl ether), aromatic ethers (e.g. diphenyl ether), cyclic ethers (e.g. dioxane);
Ketones, eg acetone; esters, especially esters of lower fatty acids with lower alkanols (eg ethyl acetate). Immediately after its formation, the new pigment described above precipitates from the reaction medium.

The products mentioned above can be used directly as crude pigments for certain purposes; however, before application they can be prepared using methods known per se, for example extraction with organic solvents or milling aids, such as salts or, in particular, which can be removed again afterwards. Trituration with hexachloroethane or reprecipitation with alkalinity is useful. With the above method, purity, tinting strength and clarity can be further improved. The novel colorants described above are valuable pigments and in finely divided form can contain polymeric organic substances such as cellulose ethers and cellulose esters, such as ethylcellulose, acetylcellulose or nitrocellulose, polyamides, polyurethanes or polyesters, natural resins or synthetic resins, such as amino resins, especially thermoplastic and thermosetting acrylic resins,
Urea-formaldehyde and melamine-formaldehyde resins, alkyd resins, phenolic resins, polycarbonates, polyolefins such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters, rubber, casein,
Used for coloring silicones and silicone resins, singly or in mixtures.

In this case, it does not matter whether the polymeric compound is present as a plastic mass or melt or in the form of a spinning solution, a lacquer or a printing ink. Depending on the end use, it may prove advantageous to use the novel pigments as toners or in the form of formulations. The new pigment is
It is characterized by its high level of sturdiness, in particular by its outstanding light, migration and weather resistance. Iminoisointrinones obtained from p-phenylenediamine are characterized by the useful yellow color that only iminoisointrinones formed from complex diamines possess.

The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example 1 6-thalol-2-cyanobenzoic acid methyl ester 5.1
9, sodium methylate 1.3 in methanol 40a
5f! Pour into a solution containing .

The above mixture is stirred at room temperature for 30 minutes, forming a clear solution. New p-phenylenediamine 1.35
9 is added and the mixture is stirred for a further 15 hours at room temperature. The yellow sodium salt of the coloring agent separates.・
The above mixture is diluted with 100 ml of o-dichlorobenzene and acidified with 5 ml of glacial acetic acid. The reaction mixture is heated to 150° C. with good stirring and methanol is distilled off. The temperature is maintained at 150°C for 2 hours. Thereafter, the mixture is left to cool to 100° C. and distributed from house to house. The wet pigment was thoroughly washed with methanol, acetone and water and placed in a vacuum oven for 10 minutes.
Dry at 0°C. Then, a yellow pigment 4.89 corresponding to the following formula is obtained. The pigments of the above formula can be used directly or in finely divided form for the coloring of plastics and plastics, after being ground with a grinding aid which can be removed after use, such as sodium chloride. I can do it.

By this method, a purely highly pigmented yellow shade with good lightfastness and migration resistance is obtained. 6-Chlor-2-cyanobenzoic acid methyl ester can be prepared, for example, by Sandmeyer reaction of 6-chloroanthranilic acid methyl ester, diazotization, and reaction with potassium cyanide.

After recrystallization from isopropanol, the pure compound is 7
It has a melting point of 6-77°C. Examples 2-9 Other pigments of the following formulas are listed in Table 1.

As mentioned in Example 1, the cyanobenzoic acid methyl ester used can be obtained from the corresponding anthranilic acid methyl ester.

Examples 10 to 18 Cyanobenzoic acid compounds listed in column 1 of the table below << Substituents X and X4 in the above formula represent the groups listed in column 1 of table 1.

The above formula is obtained by condensing 2 moles of the o-cyanobenzoic acid ester listed in column 1 of Table 1 with 1 mole of p-phenylenediamine according to the method of Example 1. In the first column of Table 1, used. - The melting point of cyanobenzoic acid ester is shown, and the second column of the same table shows the color tone of polyvinyl chloride (hereinafter abbreviated as PVC) containing 0.2% of each pigment produced. Pigments with similar good properties are obtained by condensing still according to the method of Example 1 in a molar ratio of 2:1 with the diamines listed in column 1 of the same table. The first column of the same table shows PVC containing 0.2% colorant.
Indicates the color tone of the sheet. In Table 1, Zeiss (Z
X measured with a spectrometer (eiss)
, indicates the color point by Y and Z coordinates.

λMa of the pigment of Example 21 in dimethylformamide
The x value was 394 nm.

Example 22 65 parts of stabilized polyvinyl chloride, 35 parts of dioctyl phthalate and 0.2 parts of the colorant obtained in Example 1 are stirred together and the mixture is then heated on a two roll calender for 140 parts. Leave to act for 7 minutes at °C.

In this way a yellow colored sheet is obtained which has very good light fastness and migration resistance. Example 23 Titanium dioxide 10y and pigment 2y produced according to the method of Example 1 were mixed with cocoa alkyd resin 26.4y1 melamine-formaldehyde resin (solids content: 50%) 24.
0y1 ethylene glycol monomethyl ether 8.8y
and 28.8f1 of xylene in a ball mill for 48 hours.

Spray the above lacquer on aluminum foil and let it stand for 3 minutes at room temperature.
Pre-drying for 0 minutes followed by heating at 120° C. for 30 minutes gives a yellow glaze coating.

Claims (1)

[Claims] Primary formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X_1, X_2, X_3 and X_4 represent hydrogen atoms or halogen atoms, and one of the substituents X_1 and X_4 represents a halogen atom, and the substituent X
If at most one of _2 and X_3 represents a halogen atom and X_1 represents a hydrogen atom, then
3 must not be a chlorine atom, or X_2 represents a cyano group or a carboxylic acid ester group, and X_1
, X_3 and X_4 represent hydrogen atoms, and V is the following formula: ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. isoindolinone represented by ] is condensed with a diamine represented by the following formula: H_2N-A_1-NH_2 (wherein A_1 represents a phenylene group or a naphthylene group) in a molar ratio of 2:1. A method for producing an iminoisoindolinone pigment represented by the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (wherein A_1 and X_1 to X_4 represent the above meanings).