JPH07304993A - New colorant and use thereof - Google Patents

Abstract

PURPOSE:To obtain a new colorant freed from light scattering and improved in transmittance characteristics and light and heat resistances by introducing a specified substituent into a chromogenic nucleus. CONSTITUTION:A compound of formula I (wherein Dye is a chromogenic nucleus) is reacted with a compound of formula II [wherein R<1> to R<8> are each H, halogeno, (un)substituted cycloalkyl; (un)substituted alkyl or (un)substituted alkoxy; R<9> and R<10> are each H or (un)substituted alkyl; and n is 1-10, provided that the total number of carbon atoms of R<9> and R<10> is 3 or larger] for 0.5-20hr at 50-200 deg.C in the presence of a base such as CaCO3 or NaOH in the presence or absence of a solvent such as an aromatic hydrocarbon, a halohydrocarbon or a sulfur-containing solvent to obtain a colorant of formula III (wherein X is a direct bond or a bivalent bonding group). 100 pts.wt. binder polymer is mixed with 1-100 pts.wt. above colorant, 1-100 pts.wt. photopolymerizable polyfunctional monomer, 0.01-100 pts.wt. photopolymerization initiator and additives such as a polymerization inhibitor to obtain a resin composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye which plays an important role in a color filter used in a display device such as a liquid crystal television or a color separation filter used in an image pickup tube, a color copying machine, a video printer and the like.

[0002]

2. Description of the Related Art Conventionally, as a filter dye, a blue dye has been used as an anthraquinone-based dye (JP-A-62-1366).
No. 04, JP-A-62-1974459), triphenylmethane type ("Development of special functional dyes and market trend", published by CMC, pages 47 to 48 in the 90's) and the like. As a red dye, anthraquinone type (JP-A-62-74960)
No.), azo type ("Development and market trends of special functional dyes in the 90's", CMC, p. 47), perinone type (JP-A-62-1)
36606), and the like, and as green dyes, anthraquinone-based dyes (JP-A 61-246258), triphenylmethane-based dyes (1990's "Development and Market Trend of Special Functional Dyes", CMC, pages 47-48). ), A phthalocyanine system (JP-A-60-24102, 61-140902, 61).
-254903, 61-254904, 64-690
4, 64-88505, JP-A-1-233401),
Known are perinone type (JP-A-62-136606), naphthoquinone type (JP-A-60-110290) and the like. As yellow pigments, azo pigments and vat dye pigments (90
1980s "Development of special functional dyes and market trends" CMC 48
Page), a water-soluble azo dye (JP-A-59-24010).
And JP-A-59-204011) are known.

However, the blue dye, anthraquinone compound, does not sufficiently transmit light around 440 nm and has a high transmittance at a wavelength of 500 nm or more, and has a broad transmittance curve. In addition, triphenylmethane type is suitable for coloring a filter using gelatin or casein as a base material because its molecule is ionized. It had poor light resistance and heat resistance. The anthraquinone compound and the perinone compound, which are the red pigments, have good durability, but have poor transmittance and lack of sharpness of color, and the azo compound is
Since it is water-soluble, it is suitable for coloring filters that use gelatin or casein as a base material, and although it was used for gelatin filters, due to the poor heat resistance and moisture resistance of the filter itself, There is a limit to use, and due to the poor light resistance, heat resistance, and humidity resistance of the dye itself,
It could not be used for general elements. As the green pigment,
A water-soluble compound having a sulfonic acid group, which is a phthalocyanine compound, is suitable for coloring a filter using gelatin or casein as a base material, and was used for a gelatin-based filter, but the heat resistance and moisture resistance of the filter itself were used. Due to poor sex, there was a limit to use. Further, the anthraquinone and naphthoquinone compounds are 500 to 600
nm light transmission was not sufficient, and the light fastness was also insufficient. Moreover, since the molecule of the triphenylmethane-based compound is ionized, it is suitable for coloring a filter using gelatin or casein as a substrate. Due to its poor heat resistance and humidity resistance, there is a limit to its use, and due to the poor light resistance, heat resistance and humidity resistance of the dye itself, it could not be used for general display devices. As the yellow pigment, azo pigments and vat dyes are used for filter production by the pigment dispersion method, and the filter obtained by the pigment dispersion method has high pattern accuracy, excellent heat resistance and light resistance. Has the drawback of.

(1) Since the pigment particles scatter light, the light transmittance is poor and the contrast is poor. (2) It is necessary to remove dust and large particles through a filter before applying a photosensitive resin in which a pigment is uniformly dispersed, which causes problems in the manufacturing process such as filter clogging due to aggregation of pigment particles. There is a point.

Further, the water-soluble azo dye is used for producing a filter by the dyeing method, and the color filter obtained by the dyeing method is excellent in pattern resolution, dimensional accuracy and light transmission and has high color brightness. . However, it uses gelatin or casein as the photosensitive resin, and thus has the drawback of insufficient heat resistance.

[0006]

DISCLOSURE OF THE INVENTION The present invention improves on the drawbacks of the conventional filters and dyes as described above,
It is to obtain a filter having excellent transmittance characteristics, light resistance, and heat resistance.

[0007]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have introduced a specific substituent, that is, a group represented by the following general formula (7), into a coloring mother nucleus. Has a solubility of 3% or more in a solvent such as ethyl cellosolve acetate, butyl cellosolve acetate,
Further, they have found that a clear filter having a solubility of 10% or more in a binder polymer, excellent transmittance characteristics without light scattering, and excellent durability can be obtained, and completed the present invention. The reason why the dye having a specific substituent represented by the general formula (7) is excellent in solubility in a solvent and a binder polymer is that a phenolic hydroxyl group, R ⁹ and R
^It was found that the presence of an alkyl group at ¹⁰ contributes, and that when either one of R ⁹ and R ¹⁰ has 3 or more carbon atoms, good solubility is exhibited.

[0008]

[Chemical 7] (In the formula (7), R ^{1 to} R ¹⁰ mean the same as the formula (1).)

In the present application, “dissolved” means that the dye exists in a monomolecular state of 0.01 μ or less. That is, the present invention relates to a novel dye represented by the formula (1) and its use.

[0010]

[Chemical 8] [In the formula (1), Dye represents a coloring mother nucleus, X represents a direct bond or a divalent linking group, and R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group. Group, a substituted or unsubstituted cycloalkyl group or a substituted or unsubstituted alkoxy group, R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and n is an integer of 1 to 10. Represents However, R ⁹
And the total carbon number of R ¹⁰ is 3 or more. ]

The novel dye of the present invention is represented by the formula (1):
It is a novel compound having a specific group, that is, a group represented by the above general formula (7). The substituents represented by R ^{1 to} R ¹⁰ in formula (1) are described below.

The unsubstituted alkyl group has 1 to 1 carbon atoms.
Any linear or branched alkyl group of 20 may be used,
Preferred are linear and branched alkyl groups having 1 to 12 carbon atoms, and more preferred are methyl group, ethyl group and n-
Propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, 1,2-dimethyl-propyl group Group, n-hexyl group, n-dodecyl group, 2-methylbutyl group,
2-methylpentyl group, 1,3-dimethyl-butyl group, 1-iso-
Propylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2-methyl-1-iso-propylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group , 2-ethylhexyl group, 3-methyl-1-iso-propylbutyl group, 2,2-dimethyl-1-iso-propyl-1-t-butylpropyl group, n-nonyl group, etc. An alkyl group is mentioned.

Examples of the substituted alkyl group include an alkoxy group, a halogen atom, a hydroxy group and a linear or branched alkyl group having 1 to 30 carbon atoms, which is substituted with an amino group, preferably an alkoxy group and a halogen atom. , A linear or branched alkyl group having 1 to 8 carbon atoms substituted with a hydroxy group and an amino group, and more preferably a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, a butoxyethyl group, γ−
Alkoxyalkyl groups such as methoxypropyl group, γ-ethoxypropyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, dimethoxymethyl group, diethoxymethyl group, dimethoxyethyl group, diethoxyethyl group,
Chlormethyl group, 2,2,2-trichloroethyl group, trifluoromethyl group, halogenated alkyl group such as 1,1,1,3,3,3-hexafluoro-2-propyl group, hydroxymethyl group,
Hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, hydroxyalkyl group such as hydroxyoctyl group, 2-N, N-dimethylaminoethyl group, 2-N, N-diethylaminoethyl group, 3-N, Examples thereof include aminoalkyl groups such as N-diethylaminopropyl group.

Further, the unsubstituted alkoxy group includes a linear or branched alkoxy group having 1 to 10 carbon atoms, preferably a linear alkoxy group having 1 to 5 carbon atoms, and more preferably Include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and the like. Examples of the substituted alkoxy group include an alkoxy group and a halogen-substituted linear or branched alkoxy group having 1 to 20 carbon atoms. Of these, preferably an alkoxy group or a straight-chain alkoxy group having 1 to 8 carbon atoms substituted with a halogen atom, and more preferably a methoxymethoxy group, a methoxyethoxy group, an ethoxyethoxy group,
Alkoxyalkoxy groups such as ethoxymethoxy group, methoxybutoxy group, ethoxybutoxy group, butoxybutoxy group, methoxy group substituted with halogen atom such as chlorine atom, bromine atom, iodine and fluorine atom, ethoxy group, propoxy group, butoxy group, pentyl An oxy group etc. are mentioned.

Examples of the unsubstituted cycloalkyl group include cycloalkyl groups having 5 to 12 carbon atoms. Preferably, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like can be mentioned. As the substituted cycloalkyl group, an alkyl group, a halogen atom and a cycloalkyl group having 1 to 20 carbon atoms substituted with an alkoxy group can be mentioned, preferably Is a methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group, a chlorine atom, a bromine atom, an iodine atom, a halogen atom such as a fluorine atom, a methoxy group, an ethoxy group,
Examples thereof include a cyclopentyl group substituted with an alkoxy group such as a propoxy group and a butoxy group, a cyclohexyl group, and a cycloheptyl group. The unsubstituted aryl group includes an aryl group having 6 to 20 carbon atoms, preferably a phenyl group, a naphthyl group, etc., and the substituted aryl group includes an alkyl group, a halogen atom and an alkoxy group. And an aryl group having 6 to 30 carbon atoms, preferably a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, and a t-butyl group, a chlorine atom, Examples thereof include a halogen atom such as a bromine atom, a fluorine atom and an iodine atom, and a phenyl group and a naphthyl group substituted with an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. As a halogen atom,
Examples thereof include chlorine atom, bromine atom, iodine atom and fluorine atom.

Examples of the coloring mother nucleus represented by Dye include azo series, anthraquinone series, phthalocyanine series, quinophthalone series, cyanine series, dicyanostyryl series, tricyanovinyl series, indoaniline series, condensed polycyclic series, indigo series, etc. Any skeleton described in the publicly known literature may be used (as the literature, "Dye Handbook", Okawara et al., Kodansha, 19
1986, "THE CHEMISTRY OF SYNTHETIC DYES", Volumes 1 to 6, by K. VENKATARAMAN, published by ACADEMIC PRESS). Specifically, the skeletons are listed below.

[0017]

[Chemical 9]

Preferred coloring mother nuclei include anthraquinone derivatives such as 1,4-bis (anilino) anthraquinone, 1,4-bis (4-ethyl2,6-dimethylanilino) anthraquinone, 1,4-bis ( 6-Bromo-2,4-dimethylanilino) anthraquinone, 1,4-bis (anilino) -5,8-dihydroxyanthraquinone, 1,5-diamino-4,8-dihydroxyanthraquinone, 1-toluylamino-4- Hydroxyanthraquinone, 1,4-diamino-2-phenylthioanthraquinone, 1-amino-2-phenoxy-4-hydroxyanthraquinone, 1-amino-4-anilino-2-phenylthioanthraquinone, etc .; quinophthalone derivatives such as CI Disperse Ye
llow 54, CI Disperse Yellow 64, etc .; azo derivatives such as diphenylazo compounds, thiazole-phenylazo compounds, isothiazole-phenylazo compounds, thiophene-phenylazo compounds, pyridine-phenylazo compounds, imidazole-phenylazo compounds, pyridone-phenylazo compounds, pyrazolone -Phenylazo compounds, benzothiazole-phenylazo compounds, benzisothiazole-phenylazo compounds and the like; phthalocyanine compounds such as α-alkoxyphthalocyanine.

Further, one of the following substituents is added to the coloring mother nucleus.
You may have ~ 8 pieces.

Methyl group, ethyl group, n-propyl group, iso-
Propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, neo-
Pentyl group, 1,2-dimethylpropyl group, n-hexyl group,
n-dodecyl group, 2-methylbutyl group, 2-methylpentyl group, 1,3-dimethylbutyl group, 1-iso-propylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethyl Pentyl group, 2-methyl-1-iso-propylpropyl group, 1
-Ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 2-methyl-1-iso-propylbutyl group, 2,2-
Dimethyl-1-iso-propyl-1-t-butylpropyl group, n-
A linear or branched alkyl group such as a nonyl group;

Methoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, γ-methoxypropyl group, γ-ethoxypropyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, dimethoxymethyl group, dimethoxymethyl group, Alkoxyalkyl groups such as ethoxymethyl group, dimethoxyethyl group, diethoxyethyl group;

Halogenated alkyl groups such as chloromethyl group, 2,2,2-trichloroethyl group, trifluoromethyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group; hydroxymethyl Groups, hydroxyethyl groups, hydroxypropyl groups, hydroxybutyl groups, hydroxypentyl groups, hydroxyoctyl groups and other hydroxyalkyl groups;

Aryl groups such as phenyl group, naphthyl group and indenyl group; methyl group, ethyl group, propyl group, iso-
Propyl group, butyl group, 2-methylpropyl group, pentyl group, linear alkyl group such as neo-pentyl group, branched alkyl group, methoxy group, ethoxy group, alkoxy group such as propoxy group,
A substituted aryl group having a halogen atom such as a chlorine atom, a fluorine atom, a bromine atom or an iodine atom, a naphthyl group or an indenyl group;

Aryloxy groups such as phenoxy group and naphthyloxy group; methyl group, ethyl group, propyl group, iso-
Propyl group, butyl group, 2-methylpropyl group, pentyl group, linear alkyl group such as neo-pentyl group, branched alkyl group, methoxy group, ethoxy group, alkoxy group such as propoxy group,
Substituted aryloxy groups such as phenoxy group and naphthyloxy group having a halogen atom such as chlorine atom, fluorine atom, bromine atom and iodine atom;

Arylthio groups such as phenylthio group and naphthylthio group; linear and branched groups such as methyl group, ethyl group, propyl group, iso-propyl group, butyl group, 2-methylpropyl group, pentyl group and neo-pentyl group Alkyl group, methoxy group, ethoxy group, alkoxy group such as propoxy group,
A substituted arylthio group such as a phenylthio group or a naphthylthio group having a halogen atom such as a chlorine atom, a fluorine atom, a bromine atom or an iodine atom;

Arylamino groups such as phenylamino group and naphthylamino group; methyl group, ethyl group, propyl group,
straight-chain or branched alkyl groups such as iso-propyl group, butyl group, 2-methylpropyl group, pentyl group, neo-pentyl group,
Alkoxy group such as methoxy group, ethoxy group and propoxy group, phenylamino group having halogen atom such as chlorine atom, fluorine atom, bromine atom and iodine atom, and substituted arylamino group such as naphthylamino group;

Methylamino group, ethylamino group, n-propylamino group, iso-propylamino group, n-butylamino group, iso-butylamino group, sec-butylamino group, t-butylamino group, n-pentyl group Amino group, iso-pentylamino group, neo-pentylamino group, 1,2-dimethylpropylamino group, n-hexylamino group, n-dodecylamino group, 2-methylbutylamino group, 2-methylpentylamino group, 1,3-
Dimethylbutylamino group, 1-iso-propylpropylamino group, 1,2-dimethylbutylamino group, n-heptylamino group, 1,4-dimethylpentylamino group, 2-methyl-1-iso
-Propylpropylamino group, 1-ethyl-3-methylbutylamino group, n-octylamino group, 2-ethylhexylamino group, 2-methyl-1-iso-propylbutylamino group, 2,2-
A linear or branched alkylamino group such as dimethyl-1-iso-propyl-1-t-butylpropylamino group or n-nonylamino group;

Dimethylamino group, diethylamino group, di
(n-propyl) amino group, di (iso-propyl) amino group, di
(n-butyl) amino group, di (iso-butyl) amino group, di (sec
-Butyl) amino group, di (t-butyl) amino group, di (n-pentyl) amino group, di (iso-pentyl) amino group, di (neo-pentyl) amino group, di (1,2-dimethylpropyl) ) Amino group, di (n-hexyl) amino group, di (n-dodecyl) amino group, di (2-methylbutyl) amino group, di (2-methylpentyl) amino group, di (1,3-dimethylbutyl) Amino group, di (1-
iso-propylpropyl) amino group, di (1,2-dimethylbutyl) amino group, di (n-heptyl) amino group, di (1,4-dimethylpentyl) amino group, di (2-methyl-1-iso -Propylpropyl) amino group, di (1-ethyl-3-methylbutyl) amino group, di (n-octyl) amino group, di (2-ethylhexyl) amino group, di (2-methyl-1-iso-propylbutyl) ) A linear or branched dialkylamino group such as amino group, di (2,2-dimethyl-1-iso-propyl-1-t-butylpropyl) amino group, di (n-nonyl) amino group; amino group; Hydroxy group;
A nitro group; a cyano group; a halogen atom such as a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.

From the viewpoint of durability, particularly preferable coloring mother nuclei include dye skeletons represented by the following general formulas (2), (5) and (6).

[0030]

[Chemical 10] (In the formula (2), R ^{1 to} R ¹⁰ have the meanings defined in the formula (1), R ¹¹ and R ¹² are each independently a hydrogen atom,
It represents an unsubstituted straight-chain or branched alkyl group having 1 to 20 carbon atoms, or a straight-chain or branched alkyl group having 1 to 30 carbon atoms, which is substituted with a halogen atom, an alkoxy group, a hydroxy group or an amino group. , Y represents a hydroxyl group, an amino group, a substituted or unsubstituted monoalkylamino group, or a substituted or unsubstituted arylamino group)

[0031]

[Chemical 11] (In the formula (5), R ^{1 to} R ¹⁰ have the meanings defined in the formula (1), and R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, an unsubstituted straight chain having 1 to 20 carbon atoms, or A branched alkyl group,
A straight-chain or branched alkyl group having 1 to 30 carbon atoms, which is substituted with a halogen atom, an alkoxy group, a hydroxy group or an amino group, an unsubstituted straight-chain or branched alkoxy group having 1 to 20 carbon atoms, or halogen. Represents a straight-chain or branched alkoxy group having 1 to 20 total carbon atoms substituted with an atom or an alkoxy group, or a halogen atom, R ¹⁶
Represents a hydrogen atom or a halogen atom, and X represents -CO.
-, - COOCH ₂ CO- or, -COOCH ₂ CH ₂
Represents CO-. )

[0032]

[Chemical 12] (In the formula (6), R ^{1 to} R ¹⁰ have the same meanings as in the formula (1), and R ¹⁷ is an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, an alkoxy group, Alternatively,
1 to 1 total carbon number substituted with a hydroxy group or an amino group
30 represents a linear or branched alkyl group, and X is —CO
- or it represents a -COOCH ₂ CO-. )

X may be any divalent linking group, preferably methylene group, ethylene group, methylethylene group, 1,2-dimethylethylene group, propylene group, butylene group, methoxymethylethylene group, hexylene. alkylene group such _{as, -COOCH 2 CO -, - COOCH} 2 C
_{H 2 CO -, - COOCH 2} CH 2 CH 2 CO -, - COO
_{CH (CH 3) CH 2 CO} -, - COOCH 2 CH (C
Diester of H ₃₎ CO-, etc., -NHCO -, - CO-
And other linking groups.

Examples of the method for synthesizing the dye represented by the general formula (1) include the following general formula (8) and the following general formula (9).
The compound represented by, for example, potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, sodium acetate, in the presence of a base such as potassium acetate, benzene, toluene, aromatic hydrocarbons such as xylene, chlorobenzene,
Halogenated hydrocarbons such as dichlorobenzene, sulfur-containing solvents such as sulfolane and dimethyl sulfoxide, amide solvents such as dimethylformamide and dimethylacetamide, cellosolve solvents such as ethyl cellosolve, methyl cellosolve and butyl cellosolve, 1,3-dimethyl-2 -50 in a solvent such as imidazolidinone or N-methylpyrrolidone or without solvent
Examples include a method of heating reaction at a temperature of ˜200 ° C. for about 0.5 to 20 hours.

Dye-Br (8) (In the formula (8), Dye represents a coloring mother nucleus.)

[0036]

[Chemical 13] (In the formula (9), R ^{1 to} R ¹⁰ mean the same as the formula (1))

The resin composition means a photoresist composition used for a color filter for LCD, a color separation filter for an image pickup tube, etc. The photoresist composition includes (1) dye, (2) binder polymer, and (3) light. It comprises a polymerizable polyfunctional monomer, (4) photopolymerization initiator, (5) other additives and the like. In addition, ethyl cellosolve acetate,
Acetates such as methyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate,
Lactic acid esters such as ethyl lactate, methyl lactate, propyl lactate, butyl lactate, ethyl pyruvate, methyl pyruvate, propyl pyruvate, butyl pyruvate and other pyruvate esters, methyl-2-n-amyl ketone, methyl ethyl ketone, cyclohexanone, etc. Ketone, butyl acetate,
It is also possible to dilute with a solvent of ester such as ethyl acetate, methyl acetate, propyl acetate, methyl-3-methoxypropionate.

(1) The dye is the binder polymer 100.
1 to 100 parts is used for each part. Preferably 10 to 4
Use 0 parts. Further, the dye of the present invention may be mixed and used, and a toning dye may be added thereto.

(2) The binder polymer imparts film forming ability to the photoresist, and the alkali developing type has an acid group (carboxy group) in the polymer and can be dissolved in an alkali developing solution. Examples of such a binder polymer include various (meth) acrylates containing methyl methacrylate as a main component, styrene, acrylonitrile, and a copolymer of (meth) acrylic acid.

(3) The photopolymerizable polyfunctional monomer is radically polymerized by the photoinitiator, is entangled with the binder polymer, and is crosslinked and cured to be insolubilized in the developing solution. The polyfunctional monomer is used in an amount of 1 to 100 parts, preferably 10 to 50 parts, based on 100 parts of the binder polymer. Examples of such polyfunctional monomers include trimethylolpropane triacrylate, polyethylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, (di) pentaerythritol (tri-hexa) acrylate, and other epoxy-based monomers. Polyfunctional (meth) acrylates such as urethane-based, ester-based, ether-based, bisphenol-based and spirane-based are available.

(4) The photopolymerization initiator has a role of generating active radicals of the initiator or sensitizer upon irradiation with ultraviolet rays to cause a radical polymerization reaction of a polyfunctional monomer having a polymerizable group such as (meth) acryloyl group. Is responsible for.
The photopolymerization initiator is used in an amount of 0.01 to 100 parts, preferably 1 to 20 parts, based on 100 parts of the binder polymer. Examples of such photopolymerization initiators include intermolecular hydrogen abstraction type such as benzophenone type, thioxanthone type and anthraquinone type and intramolecular bond cleavage type such as acetophenone type and benzoin ether type.

(5) Examples of other additives include hydroquinone-based and bisphenol-based polymerization inhibitors.

As a method for producing a color filter for LCD and a color separation filter for an image pickup tube using the dye of the present invention, a photosensitive resin or a photopolymerizable monomer is used to form a film on a substrate by casting, spin coating or the like. , A method of dyeing the resin layer by dipping with a dye after patterning by light irradiation, a method of patterning the dye layer by vapor deposition by a dry etching method or a lift-off method, a dye which is previously dissolved or dispersed in a photosensitive resin or a photopolymerizable monomer. Examples thereof include a method of forming a film on the substrate by casting, spin coating, etc., and patterning by light irradiation, a method of patterning by a printing method, and the like.

The patterning of the dye layer as described above can be performed on an optically transparent substrate, and the dye layer can be patterned as a substrate to be used, and the formed color filter has a predetermined function. There is no particular limitation as long as it has one.

For example, glass plate, polyvinyl alcohol, hydroxyethyl cellulose, polymethyl methacrylate, polyester, polybutyral, polyamide,
Polyethylene, polyvinyl chloride, polyvinylidene chloride,
Resin film such as polycarbonate, copolymer resin containing polyolefin, copolymer resin containing polyvinyl chloride, copolymer resin containing polyvinylidene chloride, copolymer resin containing polystyrene, or the like. There is a board. It is also possible to form the pattern-shaped dye layer integrally with the one applied as a color filter. Examples of the substrate in that case are a cathode ray tube display surface, a light receiving surface of an image pickup tube, a wafer on which a solid-state image pickup element is formed, a contact image sensor using a thin film semiconductor, a liquid crystal display surface, a photoconductor for color electrophotography, and the like. Is mentioned.

A typical method of forming a filter will be described below with reference to FIG. 1 by taking a case of forming a stripe filter as an example.

First, on a glass substrate 1 [FIG. 1 (A)] on which a black matrix 2 had been formed in advance, 20 parts of a photoresist composition was diluted with 80 parts of a solvent to prepare 100 parts of a solution, and the dye 1 to 1 of the present invention was added. A resin composition having 20 parts dissolved or dispersed is spin-coated using a spinner [Fig. 1
(B)]. Although the thickness of the resist layer 3 is determined according to desired spectral characteristics, it is usually 0.5 to 100 μm,
More preferably, it is 1 to 2 microns. After coating, the resist layer 3 is pre-baked under an appropriate temperature condition (step 1).
Then, a light or electron beam having resist sensitivity (see FIG.
Then, the resist layer 3 is exposed to light through a photomask 4 having a predetermined pattern shape corresponding to the pattern (stripe pattern) to be formed [FIG.
(C), step 2], and this is further developed to form a colored pattern 5 [FIG. 1 (D)]. If necessary, pretreatment for the purpose of relaxing the distortion of the resist layer before development, after development,
A rinse treatment may be performed to suppress the expansion of the film. Finally, post baking is performed under an appropriate temperature condition (step 3).

When a color filter having two or more colors is formed, the above steps are repeated using dyes corresponding to the respective colors as necessary, that is, depending on the number of colors of the filter used. By doing so, a multi-color color filter can be formed (note that FIG. 1 (E) shows three colored patterns 5, 6, and 7 of RGB). When forming the black matrix 2, it is preferable to perform it before forming the dye layer.

As a method for producing a color filter for use in a color copying machine or the like using the dye of the present invention,
For example, polystyrene, polymethylmethacrylate,
Polycarbonate, polyester, polyvinyl chloride, polyacetal, polyphenylene oxide, polybutylene terephthalate, polyethylene terephthalate, vinyl alcohol copolymer, polysulfone, polyphenylene sulfide, polyamideimide, polyetherimide, polyetheretherketone, etc. 0.1 to 10 parts of the dye is mixed with 100 parts of the resin to prepare by a method such as injection molding or stretching, or the dye of the present invention is dissolved alone or with a binder in a solvent, cast on the substrate, spin coating, etc. To form a film by
There is a method in which a film is formed on a substrate by vapor deposition, or after a dye is mixed with a varnish containing a polyimide resin intermediate, it is heat-treated to be resinized and processed.

The substrate may be any optically transparent resin. For example, glass plate, polyacrylic resin, polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polycarbonate resin, polyethylene resin, copolymer resin containing polyolefin, copolymer resin containing polyvinyl chloride, Examples thereof include a copolymer resin containing polyvinylidene chloride and a copolymer resin containing polystyrene.

[0051]

EXAMPLES The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 10 parts of 1-amino-2,4-dibromoanthraquinone, 50 parts of m-toluidine and 11.8 parts of sodium acetate were reacted at 130 ° C. for 5 hours. The reaction solution is an aqueous methanol solution 100
It was discharged to 0 part to obtain 9.5 parts of the following compound (10).

[0053]

[Chemical 14]

After stirring 18.4 parts of 4,4′-butylidene bis (6-t-butyl-m-cresol), 7.2 parts of potassium carbonate and 100 parts of sulfolane at 100 ° C. for 30 minutes, the compound (10) was obtained. Was added and reacted at 120 ° C. for 4 hours. The reaction mixture was discharged into 1000 parts of 50% methanol water, and the precipitated solid was separated by filtration and dried. By column purification, 7 parts of the following compound (11) was obtained.

[0055]

[Chemical 15] Melting point 136-164 [deg.] C. visible absorption; [lambda] max = 600 nm [epsilon] g = 2.0 * 10 < ⁴ > ml / g. cm (solvent; toluene)

1 g of the anthraquinone compound (11) was used as a prepolymer (manufactured by Dainippon Ink and Co., Ltd., trade name SD-17) 10
It was dissolved in g and spin coated on a glass substrate using a spinner. After drying, prebaking was performed at 85 to 100 ° C. for 2 to 5 minutes, and exposure (20 to 30 mj / cm ² , 2 minutes) was performed with a high-pressure mercury lamp through a mask having a stripe pattern. Further, this was developed to form a pattern. Finally 200
Post-baking was performed at ˜230 ° C. for 10 to 30 minutes to obtain a blue stripe filter. The thickness of the dye layer was 2.1 microns.

The filter had good durability and transmittance characteristics. The transmittance characteristics are shown in FIG.

Example 2 1 part of 1-amino-2,4-dibromoanthraquinone, 10 parts of cyclohexylamine and 11.8 parts of sodium acetate were added.
The reaction was carried out at 30 ° C for 5 hours. The reaction solution was discharged into 1000 parts of an aqueous methanol solution to obtain 9.0 parts of the following compound (12).

[0059]

[Chemical 16]

After stirring 18.4 parts of 4,4′-butylidenebis (6-t-butyl-m-cresol), 7.2 parts of potassium carbonate and 100 parts of sulfolane at 100 ° C. for 30 minutes, the compound (12) was added. Was added and reacted at 120 ° C. for 4 hours. The reaction mixture was discharged into 1000 parts of 50% methanol water, and the precipitated solid was separated by filtration and dried. By column purification, 8.3 parts of the following compound (13) was obtained.

[0061]

[Chemical 17] Visible absorption; λmax = 596 nm εg = 1.9 × 10 ⁴ ml / g. cm (solvent; toluene)

In a container equipped with a stirrer and a nitrogen introducing tube, 4,4'-bis (2-aminophenoxy) biphenyl 36.
Insert 8 parts and 202 parts of N, N-dimethylformamide, and add 39.8 parts of 4,4 '-(p-phenylenedioxy) diphthalic dianhydride in portions at room temperature under a nitrogen atmosphere for 20 hours. It was stirred. To the polyamic acid solution thus obtained, 3.0 parts of the compound (13) was added, mixed, cast on glass, and heat-treated at 200 ° C. for 5 hours. The filter thus obtained had good transmittance characteristics and excellent heat resistance and humidity resistance. Figure 3 shows the transmittance characteristics
Shown in.

Example 3 1-Amino-2,4-dibromoanthraquinone (10 parts), 2,4-xylidine (50 parts) and sodium acetate (11.8 parts) were added at 130 ° C.
Was reacted for 5 hours. The reaction solution is an aqueous methanol solution 10
It was discharged to 00 parts to obtain 9.3 parts of the following compound (14).

[0064]

[Chemical 18]

After stirring 18.4 parts of 4,4′-butylidene bis (6-t-butyl-m-cresol), 7.2 parts of potassium carbonate and 100 parts of sulfolane at 100 ° C. for 30 minutes, the compound (14) Was added and reacted at 120 ° C. for 4 hours. The reaction mixture was discharged into 1000 parts of 50% methanol water, and the precipitated solid was separated by filtration and dried. By column purification, 8.0 parts of the following compound (15) was obtained.

[0066]

[Chemical 19] Visible absorption; λmax = 602 nm εg = 1.9 × 10 ⁴ ml / g. cm (solvent; toluene)

A filter was prepared by adding 1 g of the anthraquinone compound (15) to 100 g of polystyrene and injection molding. This filter had good durability and transmittance characteristics. The transmittance characteristics are shown in FIG.

Comparative Example 1 A filter was prepared in the same manner as in Example 3 except that the dye disclosed in JP-A-62-1197459 was used. The characteristics of this filter are shown in Table 1, and the transmittance spectrum of the filter is shown in FIG.

Comparative Example 2 A filter was prepared by coloring gelatin with Acid Blue 90. The characteristics of the gelatin filter are shown in Table 1, and the transmittance characteristics of the gelatin filter are shown in FIG.

The measurement method of each measurement item and the display of the measurement result are as follows. 1. Transmittance characteristics (maximum transmittance wavelength ± 80) nm when transmittance is 10% or less, maximum transmittance is 80% or more ○ (maximum transmittance wavelength ± 80) nm, transmittance is 10% When the maximum transmittance is 70% or less when: Humidity resistance Humidity 80%, 60 ° C., 100 hours, color difference ΔE ≦ 3 ○ ΔE ≧ 5 × 3. Light resistance Fade meter at 60 ° C. for 100 hours, color difference ΔE ≦ 3 ○ ΔE ≧ 5 × 4. Heat resistance 250 ° C., color difference in 1 hour ΔE ≦ 3 ○ ΔE ≧ 5 ×

[0071]

[Table 1] (Note-1) Produced in the same manner as in Example 3 using the dye of JP-A-62-1974459 (the following structural formula).

[0072]

[Chemical 20] (Note-2) 90's "Development of special functional dyes and market trends" Filter that dyes Acid Blue 90, p48 dye published by CMC, with gelatin.

Example 4 130 parts of 1-amino-2,4-dibromoanthraquinone (10 parts), ethanolamine (50 parts) and sodium acetate (11.8 parts) were added.
The reaction was carried out at 0 ° C for 5 hours. The reaction solution was discharged into 1000 parts of a 50% aqueous methanol solution, and the following compound (16) was added to 9.0.
I got a copy.

[0074]

[Chemical 21]

After stirring 18.4 parts of 4,4′-butylidene bis (6-t-butyl-m-cresol), 7.2 parts of potassium carbonate and 100 parts of sulfolane at 100 ° C. for 30 minutes, the compound ( 16 parts of 16) was added, and the mixture was further reacted at 120 ° C. for 4 hours. The reaction solution was discharged into 1000 parts of 50% aqueous methanol solution, filtered and dried. By column purification, 8.2 parts of the following compound (17) was obtained.

[0076]

[Chemical formula 22] Visible absorption; λmax = 595 nm, εg = 2.1 × 10 ⁴ ml / g · cm (solvent; toluene) Anthraquinone compound (17) on 100 g of polystyrene
A filter was produced by adding 1 g and injection molding. This filter had good durability and transmittance characteristics.

Example 5 1-Amino-2-bromo-4-hydroxyanthraquinone 10
Parts, 4,4'-butylidene bis (6-tert-butyl-m-cresol) 12 parts, potassium hydroxide 3.52 parts with sulfolane 5
The reaction was carried out at 80 ° C. for 3 hours in 0 part. The reaction solution was discharged into 500 parts of methanol to give an anthraquinone compound (18).
8.9 parts were obtained.

[0078]

[Chemical formula 23] Visible absorption; λmax = 515 nm, εg = 2.4 × 10 ⁴ ml / g · cm (solvent; toluene)

Compound (18) in 100 parts of polyvinyl chloride
A filter was produced by adding 1 part and injection molding. This filter was good in both durability and transmittance characteristics. The characteristics of the filter are shown in Table 2 and the transmittance characteristics of the filter are shown in FIG.

Example 6 4,4'-butylidene bis (2-t-butylphenol) 22.3
Parts, 4.8 parts potassium carbonate and 100 parts sulfolane 80 parts
After stirring at 30 ° C for 30 minutes, 10 parts of 1-amino-2-bromo-4-hydroxyanthraquinone was added, and the mixture was further added at 125 ° C for 6 minutes.
Reacted for hours. The reaction mixture was poured into ice water in 1000 parts, and the precipitated solid was filtered off and dried. By column purification, 13 parts of the following compound (19) was obtained.

[0081]

[Chemical formula 24] Visible absorption: λmax = 515 nm, εg = 2.0 × 10 ⁴ ml / g · cm (solvent: toluene) 1 part of the anthraquinone compound (19) is used in the following composition

[0082]

[Chemical 25] It was dissolved in 25 parts and spin coated on a glass substrate using a spinner. After drying, prebaking was performed at 85 to 100 ° C. for 2 to 5 minutes, and exposure (20 to 30 mj / cm ² , 2 minutes) with a high pressure mercury lamp was performed through a mask having a striped pattern. Further, this was developed to form a pattern. Finally, post-baking was performed at 200 to 230 ° C. for 10 to 30 minutes to obtain a red striped filter. The thickness of the dye layer is 2.2.
It was micron.

This filter was excellent in durability and transmittance characteristics. The transmittance characteristics are shown in FIG.

Comparative Example 3 The following dyes described in JP-A-62-108068 were used,
A filter was produced by the same method as in Example 6. The characteristics of the filter are shown in Table 2, and the transmittance characteristics of the filter are shown in FIG. In the obtained filter, the dye was insoluble in the binder polymer and solid was deposited.

[0085]

[Chemical formula 26]

[0086]

[Table 2] (Note-1) Produced in the same manner as in Example 6 using the dye disclosed in JP-A-62-108068.

Example 7 The following compound (20) was placed in a container equipped with a stirrer, a reflux condenser and a nitrogen introducing tube.

[0088]

[Chemical 27] 10 parts, 1,8-diazabicyclo [5.4.0] -7-undecene 2.
8 parts and 100 parts of n-amyl alcohol were charged, and the temperature was raised to 110 ° C. under a nitrogen atmosphere. Next, at the same temperature, 0.6 part of cuprous chloride was added and reacted at 110 to 120 ° C. for 8 hours. After completion of the reaction, the reaction solution was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to remove the solvent and then purified by column to obtain 9.2 parts of a mixture of the following compound (21) and its isomer.

[0089]

[Chemical 28] Visible absorption: λmax = 706 nm, εg = 1.0 × 10 ⁵ ml / g · cm (solvent: toluene)

In a container equipped with a stirrer and a nitrogen introducing tube, 4,4'-bis (2-aminophenoxy) biphenyl 36.
8 parts and 202 parts of N, N-dimethylformamide were inserted, and 39.8 parts of 4,4 ′-(p-phenylenedioxy) diphthalic acid dianhydride was added in portions at room temperature under a nitrogen atmosphere for 20 hours. It was stirred. To the polyamic acid solution thus obtained, 3.0 parts of the compound (21) was added, mixed, cast on glass, and heat-treated at 200 ° C. for 5 hours. The filter thus obtained had good transmittance characteristics and excellent heat resistance and humidity resistance. Figure 1 shows the transmittance characteristics
It shows in 0.

Example 8 The following compound (22) was placed in a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube.

[0092]

[Chemical 29] 10 parts, 1,8-diazabicyclo [5.4.0] -7-undecene 3.
2 parts and 100 parts of n-amyl alcohol were charged and the temperature was raised to 110 ° C. under a nitrogen atmosphere. Next, 1.1 parts of palladium chloride was added at the same temperature, and the mixture was heated at 110 to 120 ° C.
Reacted for hours. After completion of the reaction, the reaction solution was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to remove the solvent, and column purification was performed to obtain 8.1 parts of a mixture of the following compound (23) and its isomer.

[0093]

[Chemical 30] Visible absorption; λmax = 703 nm, εg = 1.1 × 10 ⁵ ml / g · cm (solvent; toluene) 1 part of phthalocyanine (23) has the following composition

[0094]

[Chemical 31] It was dissolved in 25 parts and spin coated on a glass substrate using a spinner. After drying, prebaking was performed at 85 to 100 ° C. for 2 to 5 minutes, and exposure (20 to 30 mj / cm ² , 2 minutes) was performed with a high pressure mercury lamp through a mask having a striped pattern. Further, this was developed to form a pattern. Finally, post baking was performed at 200 to 230 ° C. for 10 to 30 minutes to obtain a striped filter. The thickness of the dye layer was 2 microns.

The filter had good durability and transmittance characteristics. The transmittance characteristics are shown in FIG.

Example 9 The following compound (24) was placed in a container equipped with a stirrer, a reflux condenser and a nitrogen introducing tube.

[0097]

[Chemical 32] 10 parts, 1,8-diazabicyclo [5.4.0] -7-undecene 3.
4 parts and 100 parts of n-amyl alcohol were charged, and the temperature was raised to 110 ° C. under a nitrogen atmosphere. Next, at the same temperature, 0.7 part of cuprous chloride was added and reacted at 110 to 120 ° C. for 8 hours. After completion of the reaction, the reaction solution was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to remove the solvent, and then column purified to obtain 10.3 parts of a mixture of the following compound (25) and its isomer.

[0098]

[Chemical 33] Visible absorption; λmax = 706 nm, εg = 0.9 × 10 ⁵ ml / g · cm (solvent: toluene)

Compound (25) in 100 parts of polyvinyl chloride
A filter was produced by adding 1 part and injection molding. This filter was good in both durability and transmittance characteristics.

Example 10 The following compound (26) was placed in a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube.

[0101]

[Chemical 34] 10 parts, 1,8-diazabicyclo [5.4.0] -7-undecene 3.
5 parts and 100 parts of n-amyl alcohol were charged, and the temperature was raised to 110 ° C. under a nitrogen atmosphere. Next, at the same temperature, 0.7 part of cuprous chloride was added and reacted at 110 to 120 ° C. for 8 hours. After completion of the reaction, the reaction solution was cooled and insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure to remove the solvent and then purified by column to obtain 9.7 parts of a mixture of the following compound (27) and its isomer.

[0102]

[Chemical 35] Visible absorption; λmax = 704 nm, εg = 1.0 × 10 ⁵ ml / g · cm (solvent; toluene)

A filter was prepared by adding 1 part of compound (27) to 100 parts of polymethylmethacrylate and injection molding. This filter was good in both durability and transmittance characteristics.

Example 11 The following compound (28) was placed in a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube.

[0105]

[Chemical 36] 10 parts, the following compound (29)

[0106]

[Chemical 37] 15.5 parts, potassium carbonate 4.3 parts, KI 0.2 parts and N,
70 parts of N-dimethylformamide was charged and reacted at 80 ° C. for 4 hours under a nitrogen atmosphere. After the reaction, ice water 10
It was discharged to 00 parts, and the precipitated solid was separated by filtration and dried. 12 parts of the following compound (30) was obtained by column purification.

[0107]

[Chemical 38] Visible absorption; λmax = 434 nm, εg = 4.7 × 10 ⁴ ml / g · cm (solvent; toluene) 1 part of azo compound (30) is used in the following composition

[0108]

[Chemical Formula 39] It was dissolved in 25 parts and spin coated on a glass substrate using a spinner. After drying, prebaking was performed at 85 to 100 ° C. for 2 to 5 minutes, and exposure (20 to 30 mj / cm ² , 2 minutes) was performed with a high pressure mercury lamp through a mask having a striped pattern. Further, this was developed to form a pattern. Finally, post baking was performed at 200 to 230 ° C. for 10 to 30 minutes to obtain a striped filter. The thickness of the dye layer was 2.1 microns. This filter had good durability and transmittance characteristics.

Example 12 The following compound (31) was placed in a container equipped with a stirrer, a reflux condenser and a nitrogen introducing tube.

[0110]

[Chemical 40] 10 parts, 15.0 parts of the compound (29), potassium carbonate 4.
5 parts, KI 0.1 part and N, N-dimethylformamide 8
0 part was charged and the reaction was carried out at 80 ° C. for 4 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was discharged into 1000 parts of ice water, and the precipitated solid was separated by filtration and dried. By column purification, 11 parts of the following compound (32) was obtained.

[0111]

[Chemical 41] Visible absorption; λmax = 432 nm, εg = 4.8 × 10 ⁴ ml / g · cm (solvent: toluene)

A filter was prepared by adding 1 part of compound (32) to 100 parts of polymethylmethacrylate and injection molding. This filter was good in both durability and transmittance characteristics.

Example 13 The following compound (33) was placed in a container equipped with a stirrer, a reflux condenser and a nitrogen introducing tube.

[0114]

[Chemical 42] 10 parts, the following compound (34)

[0115]

[Chemical 43] 9.9 parts, potassium carbonate 3.7 parts, KI 0.3 parts and N, N-
80 parts of dimethylformamide was charged and reacted at 80 ° C. for 4 hours under a nitrogen atmosphere. After the reaction, ice water 10
It was discharged to 00 parts, and the precipitated solid was separated by filtration and dried. By column purification, 11.2 parts of the following compound (35) was obtained.

[0116]

[Chemical 44] Visible absorption; λmax = 435 nm, εg = 4.6 × 10 ⁴ ml / g · cm (solvent: toluene)

Compound (35) in 100 parts of polyvinyl chloride
A filter was produced by adding 1 part and injection molding. This filter was good in both durability and transmittance characteristics.

Example 14 The following compound (36) was placed in a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube.

[0119]

[Chemical formula 45] 10 parts, the following compound (37)

[0120]

[Chemical formula 46] 18.3 parts, potassium carbonate 4.5 parts, KI 0.2 parts and N,
100 parts of N-dimethylformamide was charged and reacted at 80 ° C. for 5 hours under a nitrogen atmosphere. After the reaction, ice water 1
It was discharged to 000 parts, and the precipitated solid was separated by filtration and dried. By column purification, 11.2 parts of the following compound (38) was obtained.

[0121]

[Chemical 47] Visible absorption; λmax = 450 nm, εg = 5.5 × 10 ⁴ ml / g · cm (solvent; toluene)

Compound (38) in 100 parts of polyvinyl chloride
A filter was produced by adding 1 part and injection molding. This filter was good in both durability and transmittance characteristics.

Example 15 10 parts of the above compound (36) and the following compound (39) were placed in a container equipped with a stirrer, a reflux condenser and a nitrogen introducing tube.

[0124]

[Chemical 48] 17.2 parts, potassium carbonate 4.4 parts, KI 0.2 parts and N,
80 parts of N-dimethylformamide was charged and the reaction was carried out at 80 ° C. for 4 hours under a nitrogen atmosphere. After the reaction, ice water 10
It was discharged to 00 parts, and the precipitated solid was separated by filtration and dried. By column purification, 11 parts of the following compound (40) was obtained.

[0125]

[Chemical 49] Visible absorption; λmax = 451 nm, εg = 5.4 × 10 ⁴ ml / g · cm (solvent; toluene) 1 g of the quinophthalone compound (40) was used in the following composition

[0126]

[Chemical 50] It was dissolved in 25 parts and spin coated on a glass substrate using a spinner. After drying, prebaking was performed at 85 to 100 ° C. for 2 to 5 minutes, and exposure with a high pressure mercury lamp (20 to 30 mj / cm ² , 2 minutes) was performed through a mask having a stripe pattern. Further, this was developed to form a pattern. Finally, post-baking was performed at 200 to 230 ° C. for 10 to 30 minutes to obtain a striped filter. The thickness of the dye layer was 2 microns. This filter had good durability and transmittance characteristics.

Example 16 The following compound (41) was placed in a container equipped with a stirrer, a reflux condenser and a nitrogen introducing tube.

[0128]

[Chemical 51] 10 parts, the following compound (42)

[0129]

[Chemical 52] 18.9 parts, potassium carbonate 4.6 parts, KI 0.3 parts and N,
80 parts of N-dimethylformamide was charged and the reaction was carried out at 80 ° C. for 4 hours under a nitrogen atmosphere. After the reaction, ice water 10
It was discharged to 00 parts, and the precipitated solid was separated by filtration and dried. 12.1 parts of the following compound (43) was obtained by column purification.

[0130]

[Chemical 53] Visible absorption; λmax = 448 nm, εg = 5.2 × 10 ⁴ ml / g · cm (solvent; toluene)

A filter was prepared by adding 1 part of compound (43) to 100 parts of polymethylmethacrylate and injection molding. This filter was good in both durability and transmittance characteristics.

[0132] Example seventeen to eighty-six R ¹ to R ¹⁰ in the general formula (1) was produced a filter using a resin shown in dye and Table 3 shown in Table 3. These filters had good durability and filter characteristics.

The abbreviations of the resins in Table 3 are as follows. References to Examples 6, 11, and 15 mean that they are the same as the resin compositions used in Examples 6, 11, and 15. PS; polystyrene, PMMA; polymethylmethacrylate, PC; polycarbonate, PE
T: Polyethylene terephthalate, PVC: Polyvinyl chloride, SD-17: Polyacrylic photosensitive resin (Dainippon Ink)

[0134]

[Table 3]

[0135]

[Table 4]

[0136]

[Table 5]

[0137]

[Table 6]

[0138]

[Table 7]

[0139]

[Table 8]

[0140]

[Table 9]

[0141]

[Table 10]

[0142]

[Table 11]

[0143]

[Table 12]

[0144]

INDUSTRIAL APPLICABILITY The dye of the present invention in which a bisphenol compound is introduced into the dye makes it possible to provide a color filter having excellent solubility in a solvent and a binder resin, and excellent transmittance characteristics and durability.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of a manufacturing process of a color filter of the present invention.

2 is a graph showing the transmittance characteristics of the filter obtained in Example 1. FIG.

FIG. 3 is a graph showing the transmittance characteristics of the filter obtained in Example 2.

FIG. 4 is a graph showing the transmittance characteristics of the filter obtained in Example 3.

FIG. 5 is a graph showing the transmittance characteristics of the filter obtained in Comparative Example 1.

FIG. 6 is a graph showing the transmittance characteristics of the filter obtained in Comparative Example 2.

7 is a graph showing the transmittance characteristics of the filter obtained in Example 5. FIG.

8 is a graph showing the transmittance characteristics of the filter obtained in Example 6. FIG.

9 is a graph showing the transmittance characteristics of the filter obtained in Comparative Example 3. FIG.

FIG. 10 is a graph showing the transmittance characteristics of the filter obtained in Example 7.

11 is a graph showing the transmittance characteristics of the filter obtained in Example 8. FIG.

[Explanation of symbols]

 1 Glass Substrate 2 Black Matrix 3 Resist Layer 4 Photomask 5, 6, 7 Coloring Pattern

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G02B 5/20 101

Claims (10)

[Claims] 1. A dye represented by the following general formula (1): [Chemical 1] (In the formula, Dye represents a chromophore, and X is a direct bond or 2
Represents a valent linking group, R ^{1 to} R ⁸ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted alkoxy group. R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and n represents an integer of 1 to 10. However, the total number of carbon atoms of R ⁹ and R ¹⁰ is 3 or more. ) 2. The dye according to claim 1, wherein in the general formula (1), Dye is an anthraquinone residue, a quinophthalone residue, an azo residue or a phthalocyanine residue, and n is 1 to 4. 3. In the general formula (1), R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, or an alkoxy group. , A straight or branched alkyl group having 1 to 30 carbon atoms substituted with a hydroxy group or an amino group, an unsubstituted cycloalkyl group having 5 to 12 carbon atoms, a total substituted with a halogen atom, an alkyl group or an alkoxy group. C5-C20 cycloalkyl group, unsubstituted C1
To 20 straight or branched alkoxy groups, or a total of 1 carbon atoms substituted with halogen atoms or alkoxy groups
Is a linear or branched alkoxy group having 20 to 20 carbon atoms, and R ⁹ and R ¹⁰ are each independently a hydrogen atom, an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or a halogen atom, an alkoxy group. The dye according to claim 2, which is a linear or branched alkyl group having a total of 1 to 30 carbon atoms, which is substituted with a hydroxy group or an amino group. 4. The dye according to claim 3, which is represented by the following general formula (2). [Chemical 2] (In the formula, R ^{1 to} R ¹⁰ have the meanings defined in claim 3, and R ¹¹ and R ¹² are each independently a hydrogen atom, an unsubstituted straight-chain or branched alkyl group having 1 to 20 carbon atoms. Or represents a linear or branched alkyl group having a total of 1 to 30 carbon atoms, which is substituted with a halogen atom, an alkoxy group, a hydroxy group or an amino group, and Y is a hydroxyl group, an amino group, a substituted or unsubstituted monoalkylamino Group or a substituted or unsubstituted arylamino group) 5. The dye according to claim 3, which is represented by the following general formula (3). [Chemical 3] (In the formula, R ^{1 to} R ¹⁰ have the meanings defined in claim 3.) 6. The dye according to claim 3, which is represented by the following general formula (4). [Chemical 4] (In the formula, R ^{1 to} R ¹⁰ have the meanings defined in claim 3, and R ¹³ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or
Represents a substituted or unsubstituted aryl group) 7. The dye according to claim 3, which is represented by the following general formula (5). [Chemical 5] (In the formula, R ^{1 to} R ¹⁰ have the meanings defined in claim 3, and R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, an unsubstituted C 1-20 linear or branched alkyl group. A halogen atom, an alkoxy group, a hydroxy group or an amino group, which is substituted with a linear or branched alkyl group having 1 to 30 carbon atoms, an unsubstituted linear or branched alkoxy group with 1 to 20 carbon atoms, or Represents a linear or branched alkoxy group having 1 to 20 total carbon atoms substituted with a halogen atom or an alkoxy group, or a halogen atom, and R ¹⁶ represents
Represents a hydrogen atom or a halogen atom, and X represents -CO-,-
Represents COOCH ₂ CO- or -COOCH ₂ CH ₂ CO-) 8. The dye according to claim 3, which is represented by the following general formula (6). [Chemical 6] (In the formula, R ^{1 to} R ¹⁰ have the meanings defined in claim 3, and R ¹⁷ is an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, an alkoxy group, or
1 to 1 total carbon number substituted with a hydroxy group or an amino group
30 represents a linear or branched alkyl group, and X is —CO
- or it represents a -COOCH ₂ CO-. ) 9. A resin composition containing the dye according to any one of claims 1 to 8. 10. A color filter containing the dye according to claim 1.