JPH08109337A - Black organic pigment and black matrix using the pigment - Google Patents

Abstract

PURPOSE: To obtain a new purely black organic pigment excellent in a matching property with resins and useful for color filter black matrixes by condensing an imino compound having a specific structure with a carbonyl compound having a hydrogen atom at the a position. CONSTITUTION: This pigment is obtained by condensation-reacting an imino compound of formula I (the ring X is aromatic group residue; R<1> , R<2> are halogen, alkyl, etc.; p, q are 0-6; but p-q=0-6) with a carbonyl compound having a hydrogen atom at the α-position. The imino compound of formula I includes 1,3-diiminoisoindoline. The carbonyl compound having the hydrogen atom at the α position includes a compound of formula II (R<3> is 1-12C aliphatic compound residue, aliphatic residue having an aromatic compound residue; h is 1-6). The above-mentioned condensation reaction is preferably performed at 120-180 deg.C for 0.5-10hr.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black organic pigment that can be used in inks, paints, coloring agents for resins, black matrix for color filters and the like, and a black matrix for color filters using the black organic pigment.

[0002]

2. Description of the Related Art Inorganic carbon black has been used in large amounts in many fields as a black pigment. However, in the field of using an organic material as its constituent component, a black organic pigment having a better matching property with the organic material is required.

The fields of application of such black organic pigments include the fields of offset, gravure and flexographic printing inks, the field of paints, the field of plastics, the field of textiles, the field of cosmetics, and the field of color filters for liquid crystal displays.

Further, since the liquid crystal display uses a backlight, it is necessary to frame the periphery of each of the red, green and blue pixels with a black matrix for the purpose of preventing the deterioration of the contrast due to light leakage and shielding the light. Chromium pigments are mainly used for this black matrix, but it is expensive and there is a problem in terms of safety.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a black organic pigment and a black matrix for a color filter which uses the black organic pigment with high safety.

[0006]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above-mentioned problems, and as a result, the general formula (1)
It has been found that a novel black pigment can be obtained by a condensation reaction between an imino compound represented by the formula and a carbonyl compound having a hydrogen atom at the α-position. Further, by using the pigment, it is possible to provide a highly safe recording and display material.

[0007]

Embedded image [In the formula, ring X represents an aromatic residue, and R ¹ and R ² are each independently a halogen atom, an alkyl group, an alkoxy group,
It represents an alkylthio group or a nitro group, and p and q each independently represent an integer of 0 to 6. However, the sum of p and q shows the integer of 0-6. That is, the black organic pigment of the present invention can be obtained as follows.

The imino compound represented by the general formula (1) and α
A carbonyl compound having a hydrogen atom at the position in an organic solvent, preferably 100 to 220 ° C, more preferably 1
The condensation reaction is carried out at 20 to 180 ° C. for 0.5 to 10 hours. Since water and ammonia are generated during the reaction, it is convenient to separate and remove only the generated water and to use an apparatus for circulating the organic solvent in the reaction system so that the reaction proceeds rapidly. After the reaction, hot filtration is performed, the precipitate on the filter paper is washed with a solvent,
The black organic pigment of the present invention can be obtained by drying.

The molar ratio of the imino compound and the carbonyl compound used in the reaction is preferably 1: 4 to 1: 0.1,
1: 2 to 1: 0.4 are more preferable.

The reaction can be carried out without a solvent, but since it is necessary to wash off the low molecular weight compound with an organic solvent, it is advantageous in terms of the process to react in the organic solvent from the beginning.

As the organic solvent which can be used in the reaction, aromatic solvents such as benzene, toluene, xylene, mesitylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene and diphenyl ether, hexanol, heptanol, octanol, decanol, Examples thereof include aliphatic alcohol solvents such as dodecanol and hexadecanol, heterocyclic solvents such as pyridine, quinoline, 1,3-dimethyl-2-imidazolidinone and sulfolane, and polar solvents such as dimethylformamide and dimethyl sulfoxide.

The following compounds can be used as the imino compound represented by the general formula (1) of the present invention.

First, as the halogen atom of R ¹ and R ² ,
Fluorine, chlorine, bromine and iodine are preferable, and chlorine and iodine are more preferable. The alkyl moiety of the alkyl group, alkoxy group or alkylthio group has 1 to 12 carbon atoms.
The alkyl group of is preferably used.

Examples of the ring X include aromatic rings such as benzene ring, naphthalene ring, biphenyl ring, anthracene ring, indene ring, fluorene ring, phenanthrene ring, acenaphthene ring and derivatives thereof, furan ring, pyrrole ring, Thiophene ring, benzofuran ring, indole ring, indazole ring, coumarone ring, benzimidazolone ring, benzothiophene ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, pyridine ring, quinoline ring, isoquinoline ring, quinazoline ring, acridine ring ,
Heterocycles such as a phenazine ring, a pyrazine ring, an oxazine ring, a xanthene ring, a purine ring, a dibenzofuran ring and a dibenzopyrrole ring, and derivatives thereof can be mentioned.

Specific examples of the imino compound include 1,3-
Diiminoisoindoline, 1,3-Diimino-4-methylisoindoline, 1,3-Diimino-5-methylisoindoline, 1,3-Diimino-5-t-butylisoindoline, 1,3-Diimino-5 -T-amylisoindoline, 1,3-diimino-5-t-octylisoindoline, 1,3-diimino-4-chloroisoindoline, 1,3-diimino-5-chloroisoindoline,
1,3-Diimino-4,5,6,7-tetrachloroisoindoline, 1,3-Diimino-4,5,6,7-tetrabromoisoindoline, 1,3-Diimino-4,5,5
6,7-Tetrafluoroisoindoline, 1,3-Diimino-4,7-dimethoxy-5,6-dichloroisoindoline, 1,3-Diimino-4-methoxyisoindoline, 1,3-Diimino-4- Ethoxyisoindoline,
1,3-diimino-4-butoxyisoindoline, 1,
3-diimino-4-hexyloxyisoindoline,
1,3-Diimino-4- (2,5-dimethylpentyloxy) isoindoline, 1,3-Diimino-5-butoxyisoindoline, 1,3-Diimino-5-hexyloxyisoindoline, 1,3-Diimino -5- (2,5
-Dimethylpentyloxy) isoindoline, 1,3-
Diimino-4-ethylthioisoindoline, 1,3-Diimino-4-butylthioisoindoline, 1,3-Diimino-4- (t-butylthio) isoindoline, 1,3
-Diimino-5-ethylthioisoindoline, 1,3-
Diimino-5-butylthioisoindoline, 1,3-diimino-5- (t-butylthio) isoindoline, 1,
3-diimino-4-nitroisoindoline, 1,3-diimino-5-nitroisoindoline, 1,3-diimino-4,5,6,7-tetrachloroisoindolinone,
1,3-diimino-4,5,6,7-tetrabromoisoindolinone, 1,3-diimino-4,5,6,7-tetrafluoroisoindolinone, 1,3-diiminobenzoisoindoline, 1,3-Diimino-6-chlorobenzoisoindoline, 1,3-Diimino-6-t-amylbenzoisoindoline, 1,3-Diimino-6-nitrobenzoisoindoline, 1,3-Diimino-4-aza Isoindoline, 1,3-Diimino-4,7-diaza Isoindoline, 1,3-Diimino-4,7-diaza-5
6-dimethylisoindoline is mentioned. These may be used alone or in combination of two or more.

According to J. Chem. Soc., 3593-3601 (1953), 1,3-diiminoisoindoline has a 1-amino-3-iminoisoindolenine structure as shown below depending on the conditions. Therefore, the corresponding 1-amino-3-iminoisoindolenin derivatives can also be used.

[0017]

Embedded image

The imino compound represented by the general formula (1) used in the present invention is commercially available for unsubstituted 1,3-diiminoisoindoline. Regarding diiminoisoindolines having a substituent, for example, JP-A-63-
According to the method disclosed in Japanese Patent No. 280083, it can be easily synthesized from the corresponding dicarboxylic acid, imide, amide or dinitrile compound.

Next, a carbonyl compound having a hydrogen atom at the α-position is a compound having at least one carbonyl group in its structure and having a hydrogen atom bonded to the adjacent carbon atom (α-position) of the carbonyl group. Specifically, the compound is selected from the group of compounds represented by the following formula group.

[0020]

[Chemical 4] [R ³ represents an aliphatic compound residue having an aliphatic compound residue or an aromatic compound residue having 1 to 12 carbon atoms, and h represents an integer of 1 to 6. ]

[0021]

Embedded image [R ⁴ and R ⁵ are each independently a hydrogen atom, a carbon number of 1 to
4 represents an alkyl group, an aralkyl group or an aromatic compound residue, and R ⁴ and R ⁵ may combine with each other to form a ring. R
⁶ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an acyl group, an aralkyl group or an aromatic compound residue. i
Represents an integer of 1 to 6. ]

[0022]

[Chemical 6] [R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an acyl group, an aralkyl group or an aromatic compound residue, and R ⁷ and R ⁸ are They may combine to form a ring. j represents an integer of 1 to 6. ]

[0023]

[Chemical 7] [K shows the integer of 1-5. ]

[0024]

Embedded image [R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an aralkyl group, a cyano group, an aromatic compound residue or -CO ₂ R
¹⁵ (R ¹⁵ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms,
Represents an aralkyl group or an aromatic compound residue). ] Here, the residue represents a monovalent group and a polyvalent group having two or more valences.

The aromatic compound residue means a hydrocarbon aromatic compound such as a benzene ring, a naphthalene ring, a biphenyl ring, an anthracene ring, an indene ring, a fluorene ring, a phenanthrene ring and an acenaphthene ring, a furan ring, a pyrrole ring, Thiophene ring, benzofuran ring, indole ring, indazole ring, coumarone ring, benzimidazolone ring, benzothiophene ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, pyridine ring, quinoline ring, isoquinoline ring, quinazoline ring, acridine ring ,
Heterocyclic aromatic compounds such as phenazine ring, pyrazine ring, oxazine ring, xanthene ring, purine ring, dibenzofuran ring, dibenzopyrrole ring and derivatives thereof.

As the halogen atom, fluorine, chlorine, bromine and iodine can be used, but fluorine and chlorine are preferable.

As the acyl group, an aliphatic acyl group such as acetyl group, propionyl group and butyroyl group and an aromatic acyl group such as benzoyl group and nicotinoyl group are preferably used.

In the aralkyl group, the alkyl part preferably has 1 to 4 carbon atoms, and the aryl part preferably has a benzene ring, a naphthalene ring, a biphenyl ring, an indene ring or the like.

Specific examples of the carbonyl compound having a hydrogen atom at the α-position include monoketones such as acetophenone,
1-phenyl-1,2-propanedione, acetylacetone, 3,4-hexanedione, 2,5-hexanedione, 1-phenyl-1,3-butanedione, 2,3-dicyano-1,4-cyclohexanedione, Dibenzoylmethane, 2,4-pentanedione, 1,3-cyclopentanedione, 1,3-hexanedione, 1,2-cyclohexanedione, 1,3-cyclohexanedione, 1,
4-cyclohexanedione, 1,2-diacetylbenzene, 1,4-cyclohexanedione-2,5-dicarboxylic acid, 1,4-cyclohexanedione-2,5-dicarboxylic acid diethyl ester, 1,4-cyclohexanedione-2 , 5-dicarboxylic acid dibutyl ester, 1,4-
Diketones such as cyclohexanedione-2,5-dicarboxylic acid dioctyl ester, triacetylmethane, 1,
1,2-triacetylethane, 1,2,3-triacetylpropane, 2,4,6-heptanetrione, 1,3
Triketones such as 5-cyclohexanetrione, 1,
1,2,2-tetraacetylethane, 1,4,5,8-
Examples include tetraketones such as decalin tetraone.
These may be used alone or in combination of two or more.

Since the black organic pigment of the present invention is pure black, there is no need for toning and no color blur occurs even when dispersed in various media. In addition, it has excellent matching properties with resins and is said to be inferior to organic pigments in light resistance, heat resistance, solvent resistance,
Since it is also excellent in water resistance, printing inks, paints,
It can be preferably used in the fields of plastics, fibers, cosmetics, rubber, and color filters.

[0031]

EXAMPLES The present invention will be described in more detail with reference to the following examples.

Example 1 5.80 g of 1,3-diiminoisoindoline and 4.4 of 1,4-cyclohexanedione
8 g was ortho-dichlorobenzene equipped with a device for removing generated water, and reacted at 130 to 145 ° C. for 30 minutes. After hot filtration, the filter cake was washed successively with ortho-dichlorobenzene and toluene and then dried to obtain a black pigment (9.54 g).

(Examples 2 to 11) The imino compound represented by the general formula (1) and the carbonyl compound having a hydrogen atom at the α-position were used as shown in Table 1 and the same as Example 1. A black pigment was obtained by the operation of. The yields are summarized in Table 1.

[0034]

[Table 1]

Example 12 Preparation of Pigment Dispersion A mixture having the following composition was dispersed with a homogenizer for 30 minutes to obtain a pigment dispersion.

[0036]

[Table 2]

The pigment dispersion thus obtained was coated on a 12-micron-thick PET film with a microgravure coater so that the film thickness after drying would be 2 microns, and dried with hot air at 60 ° C. to obtain a black photosensitive resin. A film was obtained. A 50-micron-thick PET film (protective sheet) subjected to a release treatment was laminated on this. Next, the surface of the black photosensitive resin from which the protective sheet was peeled off and the surface of the glass substrate treated with the silane coupling agent were bonded together by a laminator heated to 60 ° C.
On a support sheet (12 micron thick PET film),
A negative film having a edging (black stripe) pattern was brought into close contact with the film and exposed to ultraviolet light of 200 mj. After exposure,
The supporting sheet was peeled off, and the glass substrate supporting the black matrix was obtained by immersing in a developing solution and removing the photosensitive resin part in the unexposed part.

[0038]

According to the present invention, a black organic pigment having a good matching property with a resin or the like was obtained. The black organic pigment is very useful especially as a recording or display material.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Bunji Sawano 1-43 Minami 1-chome, Yugemachi, Yao City, Osaka Prefecture Yamamoto Kasei Co., Ltd.

Claims (2)

[Claims] 1. A compound represented by the general formula (1): [In the formula, ring X represents an aromatic residue, and R ¹ and R ² are each independently a halogen atom, an alkyl group, an alkoxy group,
It represents an alkylthio group or a nitro group, and p and q each independently represent an integer of 0 to 6. However, the sum of p and q shows the integer of 0-6. ] The black organic pigment obtained by the condensation reaction of the imino compound represented by these, and the carbonyl compound which has a hydrogen atom in the (alpha) -position. 2. A black matrix for a color filter, which uses the black organic pigment according to claim 1.