KR20100071933A - Photosensitive composition color filter and liquid crystal display device - Google Patents

Abstract

PURPOSE: A photosensitive composition, a color filter having a colored domain which is formed using the same, and a liquid crystal display device including the color filter are provided to obtain high sensitivity at a wavelength of 365nm or 405nm and to form a hardened film which is capable of controlling the coloring. CONSTITUTION: A photosensitive composition contains a polymerizable compound, a binder resin, and a photopolymerization initiator which is marked as a chemical formula 1. In the chemical formula 1, R and B show a univalent substituent and A shows a divalent organic group. Ar shows an aryl group and Y shows an oxygen atom or a carbonyl group. The photopolymerization initiator is included in the amount of 0.1~40 mass units based on the 100 mass unit of the photosensitive composition.

Description

Photosensitive compositions, color filters, and liquid crystal displays {PHOTOSENSITIVE COMPOSITION, COLOR FILTER, AND LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a photosensitive composition, a color filter manufactured using the same, and a liquid crystal display device having the color filter.

Color filters are an integral component of liquid crystal displays. Compared with CRT displays, liquid crystal displays are more compact, more power-saving, and moreover equivalent to CRT displays in terms of performance. Thus, liquid crystal displays have been replaced by CRTs as display devices for television screens and personal computer screens.

Background Art In recent years, liquid crystal displays have been enlarged and developed in TV applications, and higher quality, i.e., higher contrast and higher color purity are required than in the prior art.

In order to improve the contrast, it is preferable to increase the content of the coloring agent (organic pigment, etc.) in the solid content of the coloring photosensitive composition in order to reduce the particle size of the coloring agent (organic pigment, etc.) used for the color filter, and to improve the color purity.

Usually, a color filter is added to alkali pigment soluble resin, a photopolymerizable compound, a photoinitiator, etc. to the pigment dispersion composition which disperse | distributed the refined pigment, and it is set as a coloring photosensitive composition, and is formed by a photolithographic method etc. using this.

If the pigment is refined for high contrast and high color purity, and the content of the pigment is high, lack of sensitivity may occur due to lack of sensitivity when the image pattern is formed by the port lithography method, or stability of the pattern size may occur. Problems such as damage were generated, and improvement was required.

In order to solve the said problem, many attempts to improve a sensitivity by the improvement of the photoinitiator used for the coloring photosensitive composition for color filters are proposed. In particular, photopolymerization initiators that are sensitive to light sources having short wavelengths (365 nm or 405 nm), have high sensitivity, have little coloration, and do not form residues when developed are desired, and as one of them, many oxime ester compounds have been proposed. (See, for example, US Patent No. 4255513, US Patent No. 4590145, Japanese Patent Application Laid-Open No. 2000-80068, Japanese Patent Application Laid-Open No. 2001-233842, and Japanese Patent Publication No. 2006-195425). However, since these oxime ester compounds have low absorbance at wavelength 365nm or 405nm, sufficient sensitivity was not obtained and further high sensitivity was desired. In addition, further improvement has been required in terms of colorability over time of the film.

Moreover, as another proposal, the technique of defining the average double bond equivalent in the organic compound which adds the binder resin and polymerizable monomer in the photosensitive composition, and specifying the molecular weight of binder resin further, and forming a forward taper shape by baking Is disclosed (see Japanese Patent Laid-Open No. 2007-93811).

However, in these techniques, the productivity in the exposure process and the development process is low, and sufficient productivity cannot be secured, and thus the price of the color filter cannot be reduced.

In order to improve the productivity of an exposure process and a developing process, exposure is performed by laser light and pattern shaping is proposed (refer Unexamined-Japanese-Patent No. 2003-287614). Unlike mercury lamps that are commonly used, lasers are expected to have high characteristics such as high straightness, high output, narrow focus, and unnecessary mask for pattern formation in the exposure process. However, even the above-described prior art did not satisfy the characteristics required for the color filter, such as roughening of the pixel surface or insufficient stability of the pattern in the development process. Moreover, in order to lower the total cost of a color filter, it is proposed not to use a large photomask as an exposure apparatus (refer Unexamined-Japanese-Patent No. 2008-76709 and Unexamined-Japanese-Patent No. 2008-51866). However, there is no suggestion of a specific material, so a proposal for a material suitable for these devices is desired.

An object of the present invention is to provide a photosensitive composition capable of forming a cured film which is highly sensitive to light having a wavelength of 365 nm or 405 nm, is excellent in storage stability, and which can suppress coloring due to heating over time.

Moreover, the objective of this invention is providing the color filter which the pattern cross section shape which uses the said photosensitive composition is favorable, and is excellent in adhesiveness with a support body, and the said color filter.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching, the composition which has favorable absorbance with respect to the light of wavelength 365nm and 405nm by using the oxime compound of a novel structure, and which can suppress coloring by the time course of heat in a cured film The knowledge that this is obtained was obtained. The specific means for solving the said subject is as follows.

<1> Photosensitive composition containing (A) polymeric compound, (B) binder resin, and (C) photoinitiator represented by following General formula (1).

In Formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and Y represents an oxygen atom or a carbonyl group.

<2> The photosensitive composition as described in <1> whose B in the said General formula (1) is a monovalent substituent selected from the group which consists of following structural formula (2)-structural formula (5).

In Structural Formula (2), X each independently represents a monovalent substituent, and Z represents an alkyl group or a phenyl group having 1 to 5 carbon atoms. n is an integer of 0-5.

<3> Photosensitive property in <1> or <2> whose content of the photoinitiator represented by said (C) following General formula (1) is 0.1-40 mass parts with respect to 100 mass parts of total solids of the said photosensitive composition. Composition.

<4> Photosensitive composition in any one of <1>-<3> which further contains (D) pigment.

<5> Photosensitive composition as described in <4> which further contains the (E) pigment dispersant.

<6> The photosensitive composition as described in <4> or <5> used for formation of the colored region of a color filter.

<7> Photosensitive composition as described in <6> in which the formation of the colored region of the said color filter is performed using the ultraviolet-ray laser of 300 nm-380 nm as an exposure source.

The color filter which has a coloring area formed on the <8> base material using the photosensitive composition as described in said <6> or <7>.

<9> The liquid crystal display device which comprises the color filter as described in said <8>.

(Effects of the Invention)

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive composition which can form the cured film which is high in the sensitivity with respect to the light of wavelength 365nm and 405nm, is excellent in storage stability, and can suppress coloring by heat-lapse | temporal aging can be provided.

Moreover, according to this invention, the pattern cross section shape which uses the said photosensitive composition is favorable, and the color filter excellent in adhesiveness with a support body, and the liquid crystal display device provided with the said color filter can be provided.

The photosensitive composition of this invention contains the (A) polymeric compound mentioned later, (B) binder resin, and (C) photoinitiator represented by following General formula (1) (henceforth called a specific oxime ester compound suitably). Moreover, the photosensitive composition for color filters which is the optimal form of the said photosensitive composition contains (D) pigment other than the said (A)-(C) component.

Hereinafter, the photosensitive composition of this invention, the photosensitive composition for color filters which is an optimal form, the color filter which uses the said photosensitive composition, and the liquid crystal display device using the said color filter are demonstrated in detail.

[Photosensitive Composition]

The photosensitive composition of this invention contains (A) polymeric compound, (B) binder resin, and (C) photoinitiator (specific oxime ester compound) represented by following General formula (1).

In Formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and Y represents an oxygen atom or a carbonyl group.

Hereinafter, each component which comprises the photosensitive composition of this invention is explained in full detail.

<(C) Photoinitiator (specific oxime ester compound) represented by General formula (1)>

The photosensitive composition of this invention contains the specific oxime ester compound represented by following General formula (1) as a (C) photoinitiator.

In Formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and Y represents an oxygen atom or a carbonyl group.

The monovalent substituent represented by R is preferably a monovalent nonmetallic atom group.

As the monovalent nonmetallic atom group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, or a substituent may have An arylsulfinyl group, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, and a substituent A phosphinoyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkylthiocarbonyl group which may have a substituent, an arylthiocarbonyl group which may have a substituent, a dialkylaminocarbonyl group which may have a substituent, and a dialkylamino which may have a substituent A thiocarbonyl group etc. are mentioned.

As an alkyl group which may have a substituent, a C1-C30 alkyl group is preferable, a C1-C10 alkyl group is more preferable, and a C1-C6 alkyl group is more preferable.

As these alkyl groups, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, sec-butyl group, t- Butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanyl phenacyl group , 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group And 3-nitrophenacyl group.

As an aryl group which may have a substituent, a C6-C30 aryl group is preferable and a C6-C15 aryl group is more preferable.

Specifically as these aryl groups, a phenyl group, a biphenyl group, 1-naphthyl group, 2-naphthyl group, 9- anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1- Indenyl group, 2-azulenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesh Tyl group, pentarenyl group, vinaphthalenyl group, ternaphthalenyl group, quarter naphthalenyl group, heptarenyl group, biphenylenyl group, indasenyl group, fluoranthhenyl group, acenaphthylenyl group, aceanthrylenyl group, phenyl Nalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group , Playadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentasenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, coronyl group, t And the like tilre naphthyl group, a heptadecyl group, a heptadecyl hexenyl group, a pyran tray carbonyl group, O-Barre group.

As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable and a C2-C5 alkenyl group is more preferable.

As these alkenyl groups, a vinyl group, an allyl group, a styryl group, etc. are mentioned specifically ,.

As an alkynyl group which may have a substituent, a C2-C10 alkynyl group is preferable and a C2-C6 alkynyl group is more preferable.

As these alkynyl groups, an ethynyl group, a propynyl group, a propargyl group, etc. are mentioned specifically ,.

As an alkylsulfinyl group which may have a substituent, a C1-C20 alkylsulfinyl group is preferable, a C1-C10 alkylsulfinyl group is more preferable, and a C1-C6 alkylsulfinyl group is more preferable.

Specific examples of these alkylsulfinyl groups include methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, hexylsulfinyl, cyclohexylsulfinyl, octylsulfinyl and 2-ethylhexylsulphi A nil group, a decanoyl sulfinyl group, a dodecanoyl sulfinyl group, an octadecanoyl sulfinyl group, a cyanomethyl sulfinyl group, a methoxymethyl sulfinyl group, etc. are mentioned.

As an arylsulfinyl group which may have a substituent, a C6-C30 arylsulfinyl group is preferable, and a C6-C14 arylsulfinyl group is more preferable.

Specific examples of these arylsulfinyl groups include phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cya Nophenyl sulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfinyl group, 4-dimethylaminophenylsulfinyl group, and the like.

As an alkylsulfonyl group which may have a substituent, a C1-C20 alkylsulfonyl group is preferable, a C1-C10 alkylsulfonyl group is more preferable, a C1-C6 alkylsulfonyl group is more preferable.

Specific examples of these alkylsulfonyl groups include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group and 2-ethylhexylsulfo And a vinyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, and perfluoroalkylsulfonyl group.

As an arylsulfonyl group which may have a substituent, a C6-C30 arylsulfonyl group is preferable, and a C6-C14 arylsulfonyl group is more preferable.

Specific examples of these arylsulfonyl groups include phenylsulfonyl group, 1-naphthylsulfonyl group, 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cya A nophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminophenylsulfonyl group, etc. are mentioned.

As an acyl group which may have a substituent, a C2-C20 acyl group is preferable, A C2-C10 acyl group is more preferable, A C2-C6 acyl group is more preferable.

Specifically as these acyl groups, for example, an acetyl group, a propanoyl group (propionyl group), butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4 -Methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl group, 2 -Butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4- A methoxy benzoyl group etc. are mentioned.

As an alkoxycarbonyl group which may have a substituent, a C2-C20 alkoxycarbonyl group is preferable, a C2-C10 alkoxycarbonyl group is more preferable, and a C2-C6 alkoxycarbonyl group is more preferable.

Specific examples of these alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, and the like. Can be mentioned.

Examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyl Oxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3 -Trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group, etc. are mentioned. have.

As a phosphinoyl group which may have a substituent, a phosphinoyl group of 2 to 50 carbon atoms is preferable, a phosphinoyl group of 2 to 20 carbon atoms is more preferable, and a phosphinoyl group of 2 to 10 carbon atoms is more preferable.

Specific examples of these phosphinoyl groups include dimethyl phosphinoyl group, diethyl phosphinoyl group, dipropyl phosphinoyl group, diphenyl phosphinoyl group, dimethoxy phosphinoyl group, diethoxy phosphinoyl group and dibenzoyl phosphino. A diary, a bis (2, 4, 6- trimethylphenyl) phosphinoyl group, etc. are mentioned.

As a heterocyclic group which may have a substituent, the aromatic or aliphatic heterocycle containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom is preferable. More preferably, it is an aromatic or aliphatic heterocycle containing a nitrogen atom, an oxygen atom, and a sulfur atom.

Specifically, for example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group , Phenoxatinyyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyridinyl group, pyramidinyl group, pyridazinyl group, indolinyl group, isoindolinyl group, 3H -Indolyl group, indolyl group, 1H-indazolyl group, furinyl group, 4H-quinolinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanyl group, quinazolinyl group , Cinnalinyl group, putridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenantridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenanyl group Narsazinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromenyl group, chromanyl group, pyrrolidi Group, pyrrolidinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, mor A polyyl group, a thioxanthone group, etc. are mentioned.

Examples of the alkylthiocarbonyl group which may have a substituent include methylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, hexylthiocarbonyl group, octylthiocarbonyl group, decylthiocarbonyl group, octadecylthiocarbonyl group, trifluoromethylthiocarbonyl group, and the like. Can be.

Examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, 4-dimethylaminophenylthiocarbonyl group, 4 -Diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group, 3-trifluoromethylphenyl A thiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group, 4-methoxyphenylthiocarbonyl group, etc. are mentioned.

Examples of the dialkylaminocarbonyl group which may have a substituent include dimethylaminocarbonyl group, diethylaminocarbonyl group, dipropylaminocarbonyl group, dibutylaminocarbonyl group and the like.

Examples of the dialkylaminothiocarbonyl group which may have a substituent include dimethylaminothiocarbonyl group, dipropylaminothiocarbonyl group, dibutylaminothiocarbonyl group and the like.

Especially, as monovalent nonmetallic atom group represented by R of General formula (1), the acyl group which may have a substituent from the point of high sensitivity is more preferable, Specifically, the acetyl group, propionyl group, benzo which may have a substituent is preferable. Diary and toluyl groups are preferable.

As a monovalent substituent represented by B in General formula (1), the aryl group which may have a substituent, the heterocyclic group which may have a substituent, the arylcarbonyl group which may have a substituent, or the heterocyclic carbonyl group which may have a substituent The aryl group which may be shown and may have a substituent is preferable. Especially, it is especially preferably a monovalent substituent selected from the group which consists of structural formula (2)-structural formula (5) shown below.

In Structural Formula (2), X each independently represents a monovalent substituent, and Z represents an alkyl group or a phenyl group having 1 to 5 carbon atoms. n is an integer of 0-5.

The monovalent substituent represented by X has an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent Aryloxy which may have a substituent, an alkylthioxy group which may have a substituent, an arylthioxy group which may have a substituent, an acyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, an arylsulfanyl group which may have a substituent, Alkylsulfinyl group which may have a substituent, Arylsulfinyl group which may have a substituent, Alkylsulfonyl group which may have a substituent, Arylsulfonyl group which may have a substituent, Acyl group which may have a substituent, Alkoxy which may have a substituent Carbonyl group, carbamoyl group which may have a substituent, sulfamoyl group which may have a substituent, amino group which may have a substituent, and May have get a good phosphino group, a substituent group may be a good heterocyclic group, a halogen atom or the like.

As an alkyl group which may have a substituent, a C1-C30 alkyl group is preferable, a C1-C10 alkyl group is more preferable, and a C1-C6 alkyl group is more preferable.

As these alkyl groups, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert- Butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanyl phenacyl group , 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group And 3-nitrophenacyl group.

As an aryl group which may have a substituent, a C6-C30 aryl group is preferable and a C6-C14 aryl group is more preferable.

Specifically as these aryl groups, a phenyl group, a biphenyl group, 1-naphthyl group, 2-naphthyl group, 9- anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1- Indenyl group, 2-azulenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesh Tyl group, pentarenyl group, vinaphthalenyl group, ternaphthalenyl group, quarter naphthalenyl group, heptarenyl group, biphenylenyl group, indasenyl group, fluoranthhenyl group, acenaphthylenyl group, aceanthrylenyl group, phenyl Nalenyl, fluorenyl, anthryl, bianthracenyl, teranthracenyl, quarter anthracenyl, anthraquinolyl, phenanthryl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl Group, playadenyl group, pisenyl group, perylenyl group, pentaphenyl group, pentasenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, coronyl group, t Tilre naphthyl and the like group, a heptadecyl group, a heptadecyl hexenyl group, a pyran group Trail, Oh-Barre group.

As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable and a C2-C5 alkenyl group is more preferable. As these alkenyl groups, a vinyl group, an allyl group, a styryl group, etc. are mentioned specifically ,.

As an alkynyl group which may have a substituent, a C2-C10 alkynyl group is preferable and a C2-C5 alkynyl group is more preferable.

As these alkynyl groups, an ethynyl group, a propynyl group, a propargyl group, etc. are mentioned specifically ,.

As an alkoxy group which may have a substituent, a C1-C30 alkoxy group is preferable, a C1-C10 alkoxy group is more preferable, and a C1-C6 alkoxy group is more preferable. Specifically as these alkoxy groups, a methoxy group, an ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group , Hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, ethoxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyloxy group , Aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarbonylmethyloxy group And N-methyl-N-benzylaminocarbonylmethyloxy group, benzyloxy group, cyanomethyloxy group and the like.

As aryloxy which may have a substituent, C6-C30 aryloxy is preferable and C6-C14 aryloxy is more preferable.

Specifically as these aryloxy, a phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, 2-part Oxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group, 4-fluorophenyloxy group, 4-cyanophenyl ox And a 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, and 4-phenylsulfanylphenyloxy group.

As an alkylthioxy group which may have a substituent, a C1-C30 thioalkoxy group is preferable, A C1-C10 thioalkoxy group is more preferable, A C1-C6 thioalkoxy group is more preferable.

Specific examples of these thioalkoxy groups include methyl thioxy group, ethyl thioxy group, propyl thioxy group, isopropyl thioxy group, butyl thioxy group, isobutyl thioxy group, sec-butyl thioxy group, tert-butyl thioxy group and pentyl. A thioxy group, an isopentyl thioxy group, a hexyl thioxy group, a heptyl thioxy group, an octyl thioxy group, 2-ethylhexyl thioxy group, a decyl thioxy group, a dodecyl thioxy group, an octadecyl thioxy group, the benzyl thioxy group, etc. are mentioned.

As an arylthioxy group which may have a substituent, a C6-C30 arylthioxy group is preferable and a C6-C14 arylthioxy group is more preferable.

Specifically as these aryl thioxy groups, a phenyl thioxy group, 1-naphthyl thioxy group, 2-naphthyl thioxy group, 2-chlorophenyl thioxy group, 2-methylphenyl thioxy group, 2-methoxyphenyl thioxy group, 2-butoxyphenylthioxy group, 3-chlorophenylthioxy group, 3-trifluoromethylphenylthioxy group, 3-cyanophenylthioxy group, 3-nitrophenylthioxy group, 4-fluorophenylthioxy group, 4-sia Nophenyl thioxy group, 4-methoxyphenyl thioxy group, 4-dimethylaminophenyl thioxy group, 4-methylsulfanylphenyl thioxy group, 4-phenylsulfanylphenyl thioxy group, and the like.

As an acyloxy group which may have a substituent, a C2-C20 acyloxy group is preferable, A C2-C10 acyloxy group is more preferable, A C2-C6 acyloxy group is further more preferable.

Specific examples of these acyloxy groups include acetyloxy group, propanoyloxy group, butanoyloxy group, pentanoyloxy group, trifluoromethylcarbonyloxy group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group etc. are mentioned.

As an alkylsulfanyl group which may have a substituent, a C1-C20 alkylsulfanyl group is preferable, A C1-C10 alkylsulfanyl group is more preferable, A C1-C6 alkylsulfanyl group is more preferable.

Specific examples of these alkylsulfanyl groups include methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, isopropylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, cyclohexylsulfanyl group, octylsulfanyl group, and 2-ethylhexylsulfanyl group. And a deylyl, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, and methoxymethylsulfanyl group.

As an arylsulfanyl group which may have a substituent, a C6-C30 arylsulfanyl group is preferable, and a C6-C14 arylsulfanyl group is more preferable.

Specific examples of these arylsulfanyl groups include phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, 2-chlorophenylsulfanyl group, 2-methylphenylsulfanyl group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group, 4-fluorophenylsulfanyl group, 4-cya Nophenyl sulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfanyl group, 4-dimethylaminophenylsulfanyl group, and the like.

As an alkylsulfinyl group which may have a substituent, a C1-C20 alkylsulfinyl group is preferable, a C1-C10 alkylsulfinyl group is more preferable, and a C1-C6 alkylsulfinyl group is more preferable.

Specific examples of these alkylsulfinyl groups include methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, hexylsulfinyl, cyclohexylsulfinyl, octylsulfinyl and 2-ethylhexylsulphi A nil group, a decanoyl sulfinyl group, a dodecanoyl sulfinyl group, an octadecanoyl sulfinyl group, a cyanomethyl sulfinyl group, a methoxymethyl sulfinyl group, etc. are mentioned.

As an arylsulfinyl group which may have a substituent, a C6-C30 arylsulfinyl group is preferable, and a C6-C14 arylsulfinyl group is more preferable.

Specific examples of these arylsulfinyl groups include phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethyl phenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4- Cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfinyl group, 4-dimethylaminophenylsulfinyl group, and the like.

As an alkylsulfonyl group which may have a substituent, a C1-C20 alkylsulfonyl group is preferable, a C1-C10 alkylsulfonyl group is more preferable, a C1-C6 alkylsulfonyl group is more preferable.

Specific examples of these alkylsulfonyl groups include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group and 2-ethylhexylsulfo And a vinyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, and methoxymethylsulfonyl group.

As an arylsulfonyl group which may have a substituent, a C6-C30 arylsulfonyl group is preferable, and a C6-C14 arylsulfonyl group is more preferable.

Specific examples of these arylsulfonyl groups include phenylsulfonyl group, 1-naphthylsulfonyl group, 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cya A nophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminophenylsulfonyl group, etc. are mentioned.

As an acyl group which may have a substituent, a C2-C20 acyl group is preferable, the C2-C10 acyl group is more preferable, and a C2-C6 acyl group is more preferable.

Specifically as these acyl groups, for example, an acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzo Diary, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl group, 2-butoxybenzoyl group , 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl group, etc. Can be mentioned.

As an alkoxycarbonyl group which may have a substituent, a C2-C20 alkoxycarbonyl group is preferable, A C1-C10 alkoxycarbonyl group is more preferable, A C1-C6 alkoxycarbonyl group is more preferable.

Specifically as these alkoxycarbonyl groups, a methoxycarbonyl group, an ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoro, for example Methyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyl Oxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3- Cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbon Group, and the like can be mentioned 4-cyanophenyl-oxy group, a 4-methoxy phenyloxy group.

As a carbamoyl group which may have a substituent, a carbamoyl group with a total of 1 to 30 carbon atoms is preferable, a carbamoyl group with a total of 1 to 10 carbon atoms is more preferable, and a carbamoyl group with a total of 1 to 6 carbon atoms is more preferable.

Specific examples of these carbamoyl groups include N-methylcarbamoyl groups, N-ethylcarbamoyl groups, N-propylcarbamoyl groups, N-butylcarbamoyl groups, N-hexylcarbamoyl groups, and N-cyclohexyl. Carbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2-chlorophenylcarbamo Diary, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N -3-cyanophenylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsul Panylphenyl carbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N- dimethylcarbamoyl group, N, N- dibutyl carbamoyl group, N, N- diphenyl carbamoyl group, etc. are mentioned. .

As a sulfamoyl group which may have a substituent, a sulfamoyl group having 0 to 30 carbon atoms is preferable, a sulfamoyl group having 0 to 10 carbon atoms is more preferable, and a sulfamoyl group having 1 to 6 carbon atoms is more preferable.

Specifically as these sulfamoyl groups, a sulfamoyl group, N-alkyl sulfamoyl group, N-aryl sulfamoyl group, N, N- dialkyl sulfamoyl group, N, N- diaryl sulfamoyl group, N- Alkyl-N-aryl sulfamoyl group etc. are mentioned. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butyl sulfamoyl group, N-hexyl sulfamoyl group, N-cyclohexyl sulfamoyl group, N-jade Tilsulfamoyl, N-2-ethylhexylsulfamoyl, N-decylsulfamoyl, N-octadecylsulfamoyl, N-phenylsulfamoyl, N-2-methylphenylsulfamoyl, N-2-chloro Phenyl sulfamoyl group, N-2-methoxyphenyl sulfamoyl group, N-2-isopropoxyphenyl sulfamoyl group, N-3-chlorophenyl sulfamoyl group, N-3-nitrophenyl sulfamoyl group, N- 3-cyanophenylsulfamoyl group, N-4-methoxyphenylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenyl Sulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N- Diphenyl sulfamoyl group etc. are mentioned.

As an amino group which may have a substituent, the C1-C50 amino group is preferable, the C1-C30 amino group is more preferable, and the C1-C15 amino group is further more preferable.

Specific examples of these amino groups include -NH ₂ , N-alkylamino groups, N-arylamino groups, N-acylamino groups, N-sulfonylamino groups, N, N-dialkylamino groups, N, N-diarylamino groups, N-alkyl-N-arylamino group, N, N- disulfonylamino group, etc. are mentioned. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-tert-butylamino group, N-hexylamino group, N-cyclohexylamino group, N- Octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino group, N-2-chlorophenylamino group, N-2 -Methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-sia Nophenylamino group, N-3-trifluoromethylphenylamino group, N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenyl Amino group, N-4-phenylsulfanylphenylamino group, N-4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-di Tylamino group, N, N-dibutylamino group, N, N-diphenylamino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N -(Dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) amino group, N, N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group, morpholino group, 3, 5-dimethyl morpholino group, a carbazole group, etc. are mentioned.

As a phosphinoyl group which may have a substituent, a phosphinoyl group of 2 to 50 carbon atoms is preferable, a phosphinoyl group of 2 to 30 carbon atoms is more preferable, and a phosphinoyl group of 2 to 15 carbon atoms is more preferable.

Specific examples of these phosphinoyl groups include dimethyl phosphinoyl group, diethyl phosphinoyl group, dipropyl phosphinoyl group, diphenyl phosphinoyl group, dimethoxy phosphinoyl group, diethoxy phosphinoyl group and dibenzoyl phosphino. A diary, a bis (2, 4, 6- trimethylphenyl) phosphinoyl group, etc. are mentioned.

As the heterocyclic group which may have a substituent, an aromatic or aliphatic heterocycle containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom is preferable, and an aromatic or aliphatic heterocycle containing a nitrogen atom, an oxygen atom, or a sulfur atom is preferable. Summoning is more preferable.

Specifically, for example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group , Phenoxatinyyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyridinyl group, pyramidinyl group, pyridazinyl group, indolinyl group, isoindolinyl group, 3H -Indolyl group, indolyl group, 1H-indazolyl group, furinyl group, 4H-quinolinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanyl group, quinazolinyl group, Cinnalinyl group, putridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenantridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenar Sazinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromenyl group, chromanyl group, pyrrolidinyl Group, pyrrolidinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, mor A polyyl group, a thioxanthone group, etc. are mentioned.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, more preferably a fluorine atom, a chlorine atom and a bromine atom, and even more preferably a chlorine atom and a bromine atom.

Especially, as a monovalent substituent represented by X of Structural formula (2), it is the alkyl group which may have a substituent, the aryl group which may have a substituent, and the alkenyl group which may have a substituent from the point of solvent solubility and the improvement of the absorption efficiency of a long wavelength region. , An alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, an arylthioxy group which may have a substituent, an amino group which may have a substituent Is preferred.

Although n in structural formula (2) represents the integer of 0-5, the integer of 0-2 is preferable.

Z in structural formula (2) represents a C1-C5 alkyl group or a phenyl group. More preferably, they are a C1-C3 alkyl group or a phenyl group, More preferably, they are a methyl group or an ethyl group.

The alkyl group which may have a substituent illustrated as a monovalent substituent represented by R in General formula (1) mentioned above and X in Structural formula (2), the aryl group which may have a substituent, and the alke which may have a substituent An alkynyl group which may have a substituent, an alkynyl group which may have a substituent, an aryloxy which may have a substituent, an alkylthioxy group which may have a substituent, an arylthioxy group which may have a substituent, and an acyl which may have a substituent Oxy group, alkylsulfanyl group which may have a substituent, arylsulfanyl group which may have a substituent, alkylsulfinyl group which may have a substituent, arylsulfinyl group which may have a substituent, alkylsulfonyl group which may have a substituent, and a substituent An arylsulfonyl group which may have, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, a carbamoyl group which may have a substituent, and a substituent The sulfamoyl group which may have, the amino group which may have a substituent, and the heterocyclic group which may have a substituent may be further substituted by the other substituent.

As such another substituent, For example, halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; Alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; Aryloxy such as phenoxy group and p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; Acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; Acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group; Alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; Arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; Alkylamino groups such as methylamino group and cyclohexylamino group; Dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group, and piperidino group; Arylamino groups such as phenylamino group and p-tolylamino group; Alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group; In addition to aryl groups such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, and phenanthryl group, hydroxy group, carboxyl group, formyl group, mercapto group, sulfo group, mesyl group, p-toluene Sulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumyl group, dimethylsulfoniumyl group, triphenylphenacylphosphoniumyl group, etc. Can be mentioned.

As a divalent organic group represented by A in General formula (1), C1-C12 alkylene which may have a substituent, the cyclohexylene group which may have a substituent, and the alkynylene group which may have a substituent are mentioned. have.

As a substituent which can be introduce | transduced into these groups, For example, Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom; Alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; Aryloxy such as phenoxy group and p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; Acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; Acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group; Arylsulfanyl groups such as alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group, phenylsulfanyl group and p-tolylsulfanyl group; Alkylamino groups such as methylamino group and cyclohexylamino group; Dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group, and piperidino group; Arylamino groups such as phenylamino group and p-tolylamino group; Alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group; In addition to aryl groups such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, and phenanthryl group, hydroxy group, carboxyl group, formyl group, mercapto group, sulfo group, mesyl group, p-toluene Sulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumyl group, dimethylsulfoniumyl group, triphenylphenacylphosphoniumyl group, etc. Can be mentioned.

Especially, as a bivalent organic group represented by A in General formula (1), since it raises a sensitivity and suppresses coloring by time-lapse | heating, an unsubstituted alkylene group and an alkyl group (for example, methyl group, an ethyl group, tert- Alkylene group substituted with butyl group, dodecyl group), Alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, The alkylene group substituted by the naphthyl group, anthryl group, phenanthryl group, and styryl group) is preferable.

As an aryl group represented by Ar in General formula (1), a C6-C30 aryl group is preferable and a C6-C14 aryl group is more preferable.

Specifically as these aryl groups, a phenyl group, a biphenyl group, 1-naphthyl group, 2-naphthyl group, 9- anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1- Indenyl group, 2-azulenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesh Tyl group, pentarenyl group, vinaphthalenyl group, ternaphthalenyl group, quarter naphthalenyl group, heptarenyl group, biphenylenyl group, indasenyl group, fluoranthhenyl group, acenaphthylenyl group, aceanthrylenyl group, phenyl Nalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group , Playadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentasenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, coronyl group, t Tilre naphthyl group, a heptadecyl group, and the like cyclohepta hexenyl group, a pyran group Trail, Oh-Barre group, may have a substituent further.

Especially, a substituted or unsubstituted phenyl group is preferable as an aryl group represented by Ar in General formula (1) from the point which raises a sensitivity and suppresses coloring by time-lapse of heating.

When the said phenyl group has a substituent, the substituent which can be introduce | transduced, for example, halogen groups, such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkoxy group, such as a methoxy group, an ethoxy group, and a tert-butoxy group, Arylthiooxy groups, such as aryloxy, such as a phenoxy group, p-tolyloxy group, an alkylthio group, such as a methyl thioxy group, an ethyl thioxy group, and a tert- butyl thioxy group, a phenyl thioxy group, and a p-tolyl thioxy group, methoxy Acyloxy groups, such as alkoxycarbonyl, acetoxy, propionyloxy, and benzoyloxy groups, such as a carbonyl group, butoxycarbonyl group, and phenoxycarbonyl group, an acetyl group, benzoyl group, isobutyryl group, acryloyl group, and methacryloyl group Alkyl sulfanyl groups, such as acyl groups, such as a methoxalyl group, a methyl sulfanyl group, and a tert- butyl sulfanyl group, an aryl sulfanyl group, such as a phenyl sulfanyl group, and a p-tolyl sulfanyl group, an alkyl, such as a methylamino group and a cyclohexylamino group Dialkylamino groups such as amino group, dimethylamino group, diethylamino group, morpholino group, piperidino group, arylamino groups such as phenylamino group, p-tolylamino group, alkyl groups such as ethyl group, tert-butyl group and dodecyl group, hydroxy group and carboxyl group , Formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, Trimethylammoniumyl group, dimethylsulfoniumyl group, triphenylphenacylphosphoniumyl group, etc. are mentioned.

Y in General formula (1) represents an oxygen atom or a carbonyl group, More preferably, it is an oxygen atom.

In general formula (1), it is preferable from the point of a sensitivity that the structure of "OAr" "COAr" formed by the aryl group represented by said Ar, and the oxygen atom or carbonyl group represented by the adjacent Y is shown below. Do.

In the compound represented by the general formula (1), a combination of preferred substituents is R is an acyl group, B is a substituent selected from the group consisting of the above structural formulas (2) to (5), and A is substituted or unsubstituted. It is an alkylene group, Ar is a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group, and Y is an oxygen atom or a carbonyl group.

In the compound represented by the general formula (1), a more preferable combination of substituents is R is an acyl group, B is a substituent represented by the above formula (2) or (3), A is an unsubstituted alkylene group, Ar is a substituted or unsubstituted phenyl group, and Y is an oxygen atom or a carbonyl group.

Hereinafter, although the specific example of the specific oxime ester compound represented by General formula (1) of this invention is shown, this invention is not limited to these.

Among the above-mentioned compounds, (I-1), (I-2), (I-3), (I-4), (I-5) from the viewpoint of solubility in a solvent and sensitivity to light of 365 nm or 405 nm ), (I-8), (I-9), (I-10), (I-11), (I-12), (I-13), (I-16), (I-17), (I-20), (I-21), (I-24), (I-25), (I-29) are preferable, and (I-1), (I-3), (I-5) , (I-8), (I-10), (I-11) and (I-12) are more preferable.

In this invention, content of (C) specific oxime ester compound (photoinitiator) is 0.1-40 mass parts with respect to 100 mass parts of total solids in the photosensitive composition for color filters, Preferably it is 0.5-20 mass parts, More preferably, It is the range of 1-15 weight part.

If content of a photoinitiator is in the said range, a polymerization reaction will advance favorably and film formation with favorable intensity | strength is possible.

<(A) Polymerizable Composition>

The polymerizable compound used in the photosensitive composition of the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. . Such a compound group is widely known in the said industrial field | area, and can be used without particular limitation in this invention. These have, for example, chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. As an example of a monomer and its copolymer, unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), its esters, and amides are mentioned. Preferably, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds and amides of unsaturated carboxylic acids and aliphatic polyamine compounds are used. Furthermore, addition reaction products of unsaturated carboxylic esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and mercapto groups with monofunctional or polyfunctional isocyanates or epoxys, and monofunctional or polyfunctional carboxyl groups Dehydration condensation reaction products with an acid, etc. are also used preferably. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, and desorption properties such as halogen groups and tosyloxy groups Substituted reactants of unsaturated carboxylic acid esters or amides having a substituent with monofunctional or polyfunctional alcohols, amines and thiols are also preferable. As another example, it is also possible to use a compound group substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the above unsaturated carboxylic acid.

Specific examples of the ester of the monomeric aliphatic polyhydric alcohol compound and unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, and propylene as acrylic acid esters. Glycol diacrylate, neopentyl glycol diacrylate, trimetholpropane triacrylate, trimetholpropane tri (acryloyloxypropyl) ether, trimethol ethane triacrylate, hexanediol diacrylate, 1, 4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol tree Acrylate, Sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid EO modified triacrylate, and the like.

As methacrylic acid ester, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimetholpropane trimethacrylate, trimethol ethane trimethacrylate, ethylene glycol di Methacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, Dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- (meta Krilloxyethoxy) phenyl] dimethylmethane and the like.

As the itaconic acid ester, ethylene glycol dietaconate, propylene glycol dietaconate, 1,3-butanediol dietaconate, 1,4-butanediol dietaconate, tetramethylene glycol dietaconate, pentaerythritol dietaconate, sorbitol tetratacoate Nate and the like.

Examples of the crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like.

As examples of other esters, for example, the aliphatic alcohol esters described in Japanese Patent Publication No. 51-47334, Japanese Patent Publication No. 57-196231, Japanese Patent Publication No. 59-5240, Japanese Patent Publication The ester which has the aromatic skeleton of Unexamined-Japanese-Patent No. 59-5241, Unexamined-Japanese-Patent No. 2-226149, the ester containing the amino group of Unexamined-Japanese-Patent No. 1-165613, etc. are used preferably. In addition, the ester monomer mentioned above can also be used as a mixture.

Moreover, as an example of the amide of an aliphatic polyhydric amine compound and unsaturated carboxylic acid of a monomer form, methylenebis- acrylamide, methylenebis-methacrylamide, 1, 6- hexamethylenebis- acrylamide, 1, 6- hexamethylenebis -Methacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like.

As an example of another preferable amide monomer, what has a cyclohexylene structure of Unexamined-Japanese-Patent No. 54-21726 is mentioned.

Moreover, the urethane type addition polymeric compound manufactured using addition reaction of an isocyanate and a hydroxyl group is also preferable, As such an example, it has two or more isocyanate groups in 1 molecule described in Unexamined-Japanese-Patent No. 48-41708, for example. The vinyl urethane compound etc. which contain two or more polymerizable vinyl groups in 1 molecule which added the vinyl monomer containing the hydroxyl group represented by following General formula (A) to a polyisocyanate compound are mentioned.

CH _{2 =} C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH (A)

(However, in formula (A), R ⁴ and R ⁵ each represent H or CH ₃ )

Moreover, urethane acrylates as described in Unexamined-Japanese-Patent No. 51-37193, Unexamined-Japanese-Patent No. 2-32293, and Unexamined-Japanese-Patent No. 2-16765, and Unexamined-Japanese-Patent No. 58-49860 Also preferred are urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Application Laid-Open No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in a molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-105238 By using it, the photopolymerizable composition which is very excellent in the photosensitive speed can be obtained.

Other examples include polyester acrylates and epoxy resins as described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490; Polyfunctional acrylates and methacrylates, such as epoxy acrylates which made (meth) acrylic acid react, are mentioned. Moreover, the specific unsaturated compound of Unexamined-Japanese-Patent No. 46-43946, Unexamined-Japanese-Patent No. 1-40337, Unexamined-Japanese-Patent No. 1-40336, and the vinyl of Unexamined-Japanese-Patent No. 2-25493 are mentioned. Phosphonic acid type compounds etc. are mentioned. In addition, in some cases, the structure containing the perfluoroalkyl group of Unexamined-Japanese-Patent No. 61-22048 is used preferably. Moreover, what was introduced as a photocurable monomer and oligomer can be used by Japanese adhesive association vol.20, No. 7, page 300-308 (1984).

About these addition polymeric compounds, the detail of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of the photosensitive composition. For example, it selects from the following viewpoints.

In terms of sensitivity, a structure having a high content of unsaturated groups per molecule is preferable, and in most cases, a bifunctional or higher function is preferable. In addition, in order to raise the intensity | strength of a cured film, a trifunctional or more thing is good, and also the sensitivity by using together the thing of another functional number and another polymeric group (for example, acrylic ester, methacrylic ester, a styrene type compound, a vinyl ether type compound) is used. The method of adjusting both strength and strength is also effective.

In addition, the selection and use of the addition polymerizable compound are important factors also in terms of compatibility and dispersibility with other components (eg, photopolymerization initiator, colorant (pigment, dye), binder polymer, etc.) contained in the photosensitive composition. For example, compatibility may be improved by using a low-purity compound and using 2 or more types together. Moreover, a specific structure can also be selected in order to improve adhesiveness with hard surfaces, such as a support body.

Content of (A) polymeric compound in the photosensitive composition is used in 5-70 mass parts when the solid content of the photosensitive composition is 100 mass parts, Preferably it is 5-50 mass parts, More preferably, it is 10-40 mass parts Used in the range of wealth.

<(B) Binder Resin>

The photosensitive composition of this invention contains (B) binder resin. As binder resin, if it is a high molecular compound soluble in a solvent, it can use without a restriction | limiting in particular. As preferable binder resin, alkali-soluble resin is preferable from the viewpoint of alkali developability by a port lithography method.

Alkali-soluble resin can also be contained in the adjustment step of a pigment dispersion composition, and can also be divided and added to the process of both adjustment of a pigment dispersion composition and adjustment step of a coloring photosensitive composition.

Alkali-soluble resins are linear organic high molecular polymers, and groups which promote at least one alkali solubility (e.g., carboxyl group, phosphoric acid group, sulfonic acid group, etc.) in a molecule (preferably an acrylic copolymer, a molecule having a styrene copolymer as a main chain) It can select suitably from alkali-soluble resin which has). Among these, More preferably, it is soluble in the organic solvent and can be developed by a weak alkali aqueous solution.

For the production of alkali-soluble resin, for example, a method by a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, radical initiator and the amount of radical initiator, solvent type, and the like when the alkali-soluble resin is produced by the radical polymerization method can be easily set by a person skilled in the art and can be experimentally determined. have.

As said linear organic high polymer, the polymer which has a carboxylic acid in a side chain is preferable. For example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, and Japanese Patent Publication No. 59-53836 Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified males as described in the respective publications of Japanese Patent Application Laid-Open No. 59-71048 Acid copolymers, acid cellulose derivatives having a carboxylic acid in the side chain, and an acid anhydride added to a polymer having a hydroxyl group, and the like, and polymer polymers having a (meth) acryloyl group in the side chain are also preferred. Can be mentioned.

Among these, in particular, a multicomponent copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid copolymer or benzyl (meth) acrylate / (meth) acrylic acid / other monomer is preferable. In addition, what copolymerized methacrylic acid 2-hydroxyethyl etc. can also be mentioned as useful. The polymer may be used in admixture in any amount.

2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and 2-hydroxy-3-phenoxypropylacrylic acid described in Japanese Patent Application Laid-Open No. 7-140654. Latex / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methylmethacrylate / methacrylic acid copolymer, 2-hydroxyethyl Methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and the like.

About the specific structural unit of alkali-soluble resin, the copolymer of (meth) acrylic acid and another monomer copolymerizable with this is preferable especially.

As another monomer copolymerizable with the said (meth) acrylic acid, alkyl (meth) acrylate, aryl (meth) acrylate, a vinyl compound, etc. are mentioned. Here, the hydrogen atom of an alkyl group and an aryl group may be substituted by the substituent.

Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth). Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, cyclohexyl acrylate Can be mentioned.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl (meth) acrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl (meth) acrylate, Polystyrene macromonomer, polymethylmethacrylate macromonomer, CH ₂ = CR ³¹ R ³² [Herein, R ³¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. And CH ₂ = C (R ³¹ ) (COOR ³³ ) [wherein R ³¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³³ represents an alkyl group having 1 to 8 carbon atoms or an aral having 6 to 12 carbon atoms; A killer group].

These copolymerizable other monomers can be used individually by 1 type or in combination of 2 or more type. Preferred copolymerizable other monomers are at least one selected from CH ₂ ═CR ³¹ R ³² , CH ₂ ═C (R ³¹ ) (COOR ³³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene, Especially preferably, CH ₂ = CR ³¹ R ³² and / or CH ₂ = C (R ³¹ ) (COOR ³³ ). These R ³¹ , R ³² and R ³³ are synonymous with the definitions of R ³¹ , R ³² and R ³³ , respectively.

As content of (B) binder resin, such as alkali-soluble resin in the photosensitive composition, 1-20 mass% is preferable with respect to the total solid of a photosensitive composition, More preferably, it is 2-15 mass%, More preferably, 3 It is -12 mass%.

[Photosensitive Composition for Color Filters]

Although the photosensitive composition of this invention makes an above-mentioned (A) polymeric compound, (B) binder resin, and (C) specific oxime ester compound an essential component, in the photosensitive composition for color filters which is an optimal form, (D) pigment is used. It contains more.

<(D) Pigment>

The photosensitive composition for color filters of this invention can obtain the coloring photosensitive composition of a desired color by containing (D) pigment. It does not specifically limit as a pigment, A conventionally well-known various pigment can be used 1 type or in mixture of 2 or more types. In the case of the photosensitive composition for color filters of the present invention, any one of chromatic colorants such as R, G, and B forming the color pixels of the color filter, and black pigments generally used for forming the black matrix can be used. Can be.

As the pigment of the chromatic system, various conventionally known inorganic pigments or organic pigments can be used. In addition, considering that the inorganic pigment or the organic pigment is preferably high transmittance, the use of as fine as possible is preferable, and considering the handling property, the average particle diameter (average primary particle diameter) of the pigment is 0.01 μm to 0.1 μm. It is preferable and 0.01 micrometer-0.05 micrometers are more preferable.

Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, metal oxides, such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and the complex oxide of the said metal are mentioned.

As an organic pigment, for example

C. I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;

C. I. Pigment Orange 36, 38, 43, 71;

C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;

C. I. Pigment Violet 19, 23, 32, 39;

C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C. I. Pigment Green 7, 36, 37, 58;

C. I. Pigment Brown 25, 28;

C. I. Pigment Black 1, 7;

Carbon black etc. are mentioned.

Especially in this invention, what has basic N atom in the structural formula of a pigment can be used preferably. Pigments having these basic N atoms exhibit good dispersibility in the photosensitive composition. Although the cause is not elucidated sufficiently, it is presumed that the good affinity of the photosensitive polymerization component and a pigment has influenced.

The following can be mentioned as a pigment which can be used preferably in this invention. However, this invention is not limited to these.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,

C. I. Pigment Orange 36, 71,

C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,

C. I. Pigment Green 7, 36, 58

C. I. Pigment Violet 19, 23, 32,

C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,

C. I. Pigment Black 1

These organic pigments can be used alone or in various combinations to increase the color purity. The specific example of the said combination is shown below.

For example, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them as a red pigment, a disazo yellow pigment, an isoindolin yellow pigment, a quinophthalone yellow pigment or peryl Mixture of a len type red pigment, etc. can be used.

For example, CI pigment red 177 is mentioned as an anthraquinone pigment, CI pigment red 155 and CI pigment red 224 are mentioned as a perylene pigment, CI pigment red 254 is a diketopyrrolopyrrole pigment. The mixture with CI pigment yellow 139 is preferable at the point of color reproducibility.

As for mass ratio (yellow pigment / red pigment) with respect to the red pigment of a yellow pigment, 5 / 100-50 / 100 are preferable. By setting it as the said range, the light transmittance of 400 nm-500 nm can be suppressed effectively, and color purity can be improved. In addition, a color can be obtained as the NTSC target color without causing a deviation in the target dominant wavelength.

Especially as said mass ratio (yellow pigment / red pigment), the range of 10 / 100-30 / 100 is optimal. In addition, when it is a combination of red pigments, the mass ratio of each red pigment can be adjusted according to chromaticity.

As the green pigment, a halogenated phthalocyanine pigment may be used alone or in combination with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindolin yellow pigment. For example, CI Pigment Green 7, 36, 37, 58, CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180 or CI Pigment. It is preferable to mix and use the cement yellow 185.

The mass ratio (yellow pigment / green pigment) of the yellow pigment to the green pigment is preferably in the range of 5/100 to 150/100. By setting it as the said range, the light transmittance of 400 nm-450 nm can be suppressed effectively, and color purity can be improved. In addition, a color can be obtained as the NTSC target color without causing a deviation in the target dominant wavelength.

As said mass ratio (yellow pigment / green pigment), the range of 30/100-120/100 is especially preferable.

As a blue pigment, a phthalocyanine type pigment can be used individually, or this and a dioxazine type purple pigment can be mixed and used. For example, it is preferable to mix C. I. pigment blue 15: 6 and C. I. pigment violet 23. The mass ratio (purple pigment / blue pigment) of the purple pigment to the blue pigment is preferably in the range of 0/100 to 30/100, more preferably 10/100 or less.

In addition, when using the photosensitive composition of this invention when forming black films, such as a black matrix, a black thing (black coloring agent) is used as a coloring agent.

In this invention, various well-known black pigment and black dye can be used as a black coloring agent. In particular, carbon black, titanium black, titanium oxide, iron oxide, manganese oxide, graphite, and the like are preferable from the viewpoint of achieving a high optical density in a small amount, and among them, at least one of carbon black and titanium black is preferable. Do.

These black coloring agents may be used individually by 1 type, or may mix and use 2 or more types.

It is preferable that the average particle diameter (average primary particle diameter) of a black pigment is small from a viewpoint of the residue suppression at the time of image development, and it is preferable that it is 30 nm or less specifically ,. Especially, in order to suppress the residue at the time of developing the color filter which requires high resolution, 5 nm-25 nm are preferable, 5 nm-20 nm are more preferable, and 5 nm-are the average primary particle diameter (particle size). 15 nm or less is especially preferable.

Although content of the black coloring agent in the total solid of a photosensitive composition is not specifically limited, In order to obtain a high optical density as a thin film, as high content as possible is preferable, 25 mass%-80 mass% are preferable, 30 mass%-75 mass % Is more preferable, and 35 mass%-70 mass% are more preferable.

If the amount of the black colorant is too small, it is necessary to increase the thickness of the film in order to obtain high optical density. If the amount of the black colorant is too large, the photocuring does not proceed sufficiently, so that the strength as a film decreases or the developing latitude becomes narrow during alkali development. have.

In the photosensitive composition, you may use multiple types of black coloring agents together. Thus, when multiple types of black coloring agents are used together and carbon black is used as the main component, the mass ratio (combination black coloring agent / carbon black to be used) to carbon black is preferably in the range of 5/95 to 40/60. , 5 / 95-30 / 70 are more preferable, and 10 / 90-20 / 80 is still more preferable. The mass of the black colorant to be used together becomes their total mass. By setting the mass ratio (combination black colorant / carbon black) to be used in combination with carbon black in the range of 5/95 to 40/60, it is possible to create a stable coating film without aggregation in the photosensitive composition and without staining.

Preferred carbon blacks for the present invention include, for example, carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, and # 850 manufactured by Mitsubishi Kagaku Corporation. , MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, diamond black A, diamond black N220M, diamond black N234, diamond black I, diamond black LI, diamond black II, diamond black N339, diamond black SH, diamond black SHA, diamond black LH, diamond black H, diamond black HA, diamond black SF, diamond black N550M, diamond black E, Diamond black G, diamond black R, diamond black N760M, diamond black LP; Carbon black thermos N990, N991, N907, N908, N990, N991, N908 available from Cancarb; Carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H , Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal; Carbon Black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2V, ColorBlack Fw1, ColorBlack Fw18, ColorBlack S170, ColorBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, PrintexU, PrintexV, Printex140U, etc. manufactured by Evonik Degussa.

It is preferable that the carbon black in this invention has insulation. Insulating carbon black is carbon black which exhibits insulation when the volume resistance as a powder is measured by the following method. For example, carbon black particles have an organic substance adsorbed, coated or chemically bonded (grafted). It means having an organic compound on the surface of black particles.

A coating liquid is prepared by dispersing in a propylene glycol monomethyl ether so that a copolymer of carbon black, benzyl methacrylate and methacrylic acid (70:30 in a molar ratio, and a mass average molecular weight of 30,000) becomes a 20:80 mass ratio. The coating liquid was applied onto a chromium substrate having a thickness of 1.1 mm and a 10 cm x 10 cm to prepare a coating film having a dry film thickness of 3 µm, and the coating film was heated at 220 ° C. for about 5 minutes in a hot plate, followed by JIS. It is applied by Mitsubishi Kagaku Co., Ltd. high resistivity meter Highrester UP (MCP-HT450) based on K 6911, and a volume resistance value is measured in the environment of 65% of 23 degreeC relative humidity. As this volume resistance value, carbon black which shows 10 ⁵ ohm * cm or more, More preferably, 10 ⁶ ohm * cm or more, More preferably, 10 ⁷ Ω * cm or more is preferable.

Moreover, as carbon black, Unexamined-Japanese-Patent No. 11-60988, Unexamined-Japanese-Patent No. 11-60989, Unexamined-Japanese-Patent No. 10-330643, Unexamined-Japanese-Patent No. 11-80583, Japan patent The resin-coated carbon black described in Unexamined-Japanese-Patent No. 11-80584, Unexamined-Japanese-Patent No. 9-124969, and Unexamined-Japanese-Patent No. 9-95625 can also be used.

Further, preferred titanium blacks for the present invention include 12S, 13M, 13M-C, 13R-N manufactured by Mitsubishi Kagaku Co., Ltd. and Tilack D manufactured by Ako Kasei Co., Ltd.

Moreover, it is preferable that the photosensitive composition of this invention containing such a black coloring agent is used in order to form black films, such as a black matrix. Since the black film has light shielding properties and antireflection properties, the black film can be applied to the production of antireflection films, light shielding films and the like in addition to the black matrix.

The pigment that can be used in the photosensitive composition is a pigment whose average particle diameter (r) (unit nm) satisfies 20 ≦ r ≦ 300, preferably 125 ≦ r ≦ 250, particularly preferably 30 ≦ r ≦ 200. desirable. By using the pigment of such average particle diameter r, red and green pixels of high contrast ratio and high light transmittance can be obtained. The "average particle diameter" here means the average particle diameter with respect to the secondary particle which the primary particle (single microcrystal) of a pigment aggregated.

In addition, the particle diameter distribution (henceforth simply called "particle diameter distribution") of the secondary particle of the pigment which can be used in this invention is 70 mass% of the whole secondary particle which enters into (average particle diameter +/- 100) nm. As mentioned above, Preferably it is 80 mass% or more.

In addition, the average primary particle diameter in this invention is a long diameter (longest diameter) and a shorter diameter with respect to 100 primary particles of the pigment which image the particle | grains in a visual field with a transmission electron microscope, and comprise the aggregate on a two-dimensional image. The average value of the diameter (short diameter) of a side is calculated | required, respectively, and it is the average value.

In order to obtain a pigment having a desired particle diameter, it is preferable to employ a solvent salt milling process in that a pigment particle can be easily suppressed and a pigment particle having a relatively small average primary particle diameter can be obtained.

This solvent salt milling means kneading and grinding of a pigment, an inorganic salt, and an organic solvent. Pigments with large particle diameters may be subjected to dry grinding and then solvent salt milling. Specifically, a pigment, an inorganic salt, and an organic solvent which does not dissolve these are put into a kneading machine, and kneading and grinding is performed therein. As a kneader at this time, kneader, a mix muller, etc. can be used, for example.

As said inorganic salt, a water-soluble inorganic salt can be used preferably, For example, it is preferable to use inorganic salts, such as sodium chloride, potassium chloride, sodium sulfate. Moreover, it is more preferable to use the inorganic salt of 0.5-50 micrometers of average particle diameters. Such inorganic salts are easily obtained by pulverizing ordinary inorganic salts.

It is preferable to use the organic solvent which can suppress crystal growth as an organic solvent. As such an organic solvent, a water-soluble organic solvent can be used preferably, For example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2- Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol Monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol, etc. can be used.

Although the usage-amount of the water-soluble organic solvent at this time is not specifically limited, 0.01-5 parts and 0.8-2 parts are preferable with respect to 1 part of pigments by mass conversion.

30-150 degreeC is preferable and, as for the temperature at the time of solvent salt milling, 80-100 degreeC is more preferable. The time for solvent salt milling is preferably 5 to 20 hours, more preferably 8 to 18 hours.

As washing | cleaning, both water washing and hot water can be employ | adopted. The number of washings may be repeated in a range of 1 to 5 times. In the case of the mixture using a water-soluble inorganic salt and a water-soluble organic solvent, the organic solvent and the inorganic salt can be easily removed by washing with water.

As said filtration sorting and drying after washing | cleaning, the batch-type or continuous drying etc. which perform dehydration of a pigment and / or a solvent by heating at 80-120 degreeC by the heating source provided in the dryer, etc. are mentioned, for example. Generally, box type dryer, band dryer, spray dryer, etc. are mentioned. In addition, the pulverization after drying is not an operation for increasing the specific surface area or decreasing the average particle diameter of the primary particles. For example, as in the case of drying using a box dryer or a band dryer, the pigments lump. When it becomes a shape etc., it is performed in order to loosen | pulverize a pigment and can mention, for example, grinding | pulverization with a mortar, a hammer mill, a disk mill, a pin mill, a jet mill, etc. are mentioned.

Pigments having the above average particle diameters and particle diameter distributions are pigment mixtures in which commercially available pigments are mixed with other pigments (average particle diameters usually exceed 300 nm) used in some cases, preferably with a dispersant and a solvent. For example, it can prepare by mixing and disperse | distributing, grind | pulverizing using grinders, such as a bead mill and a roll mill. The pigment thus obtained usually takes the form of a pigment dispersion.

As content of the pigment contained in the photosensitive composition, it is preferable that it is 30-95 mass% in the total solid of a photosensitive composition, 40-90 mass% is more preferable, 50-80 mass% is more preferable.

When there is too little coloring agent, there exists a tendency for suitable chromaticity to not be obtained when a color filter is produced with the photosensitive composition. On the other hand, when too much, photocuring does not fully advance, the intensity | strength as a film | membrane falls, and the development latitude at the time of alkali image development tends to become narrow. However, since the (C) specific oxime ester compound (photoinitiator) used for this invention has high light absorption efficiency, even if it contains a coloring agent in high concentration in a photosensitive composition, a sensitivity improvement effect is exhibited notably.

<(E) Pigment Dispersant>

It is preferable that the photosensitive composition of this invention adds the (E) pigment dispersant from a viewpoint of improving the dispersibility of a pigment.

Examples of the pigment dispersant usable in the present invention include polymer dispersants [e.g., polyamideamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates. , (Meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkylinic acid ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative, and the like.

Polymeric dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers from the structure.

The polymeric dispersant adsorbs on the surface of the pigment and acts to prevent reagglomeration. Therefore, the terminal modified | denatured polymer | macromolecule, graft-type polymer, and block polymer which have anchor site | part to a pigment surface are mentioned as a preferable structure.

On the other hand, the pigment derivative has the effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

Specific examples of the pigment dispersant that can be used in the present invention include "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing acid group), 130 (polyamide), 161 manufactured by BYK Chemie. , 162, 163, 164, 165, 166, 170 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)," EFKA4047, 4050, 4010, 4165 (polyurethane type), made by EFKA, EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (Azo pigment derivative), "Azisper PB821, PB822" made by Ajinomoto Fine Techno Co., Ltd., "Florene TG-710 (urethane oligomer)" made by Kyogisha Co., Ltd., "Polyflow No. 50E, No. 300 (acrylic-based aerial system) ") Disparon KS-860, 873SN, 874, # 2150 (aliphatic) Divalent carboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725 '', `` demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN- B (aromatic sulfonic acid formalin polycondensate), "homogenol L-18 (polymeric polycarboxylic acid)", "emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "acetamine 86 ( Stearylamine Acetate) ", Lubrizol Corporation" Solpers 5000 (phthalocyanine derivative), 22000 (Azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the terminal), 24000, 28000 , 32000, 38500 (graft polymer), Nikko T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) manufactured by Nikko Chemical.

These dispersing agents may be used independently and may be used in combination of 2 or more type. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.

As content of the (E) pigment dispersing agent in the photosensitive composition, it is preferable that it is 1-80 mass% with respect to a pigment, 5-70 mass% is more preferable, 10-60 mass% is further more preferable.

Specifically, in the case of using a polymer dispersant, the amount thereof is preferably in the range of 5 to 100% by mass and more preferably in the range of 10 to 80% by mass with respect to the pigment.

Moreover, when using a pigment derivative, as the usage-amount, it is preferable to exist in the range of 1-30 mass% with respect to a pigment, It is more preferable to exist in the range of 3-20 mass%, and to the range of 5-15 mass% It is particularly desirable to have.

When using a coloring agent (pigment) and a dispersing agent in a photosensitive composition, it is preferable that the sum total of a coloring agent and a dispersing agent content is 30 mass% or more and 90 mass% or less with respect to the total solid which comprises a photosensitive composition from a viewpoint of hardening sensitivity and color concentration, It is more preferable that they are 40 mass% or more and 85 mass% or less, and it is still more preferable that they are 50 mass% or more and 80 mass% or less.

The photosensitive composition of this invention can use together a photoinitiator, a sensitizer, and a sensitizer further as needed.

<Other photopolymerization initiator>

The photosensitive composition of this invention can use another photoinitiator together. For example, halomethyl-oxadiazole described in Japanese Patent Publication No. 57-6096, Halomethyl-s-triazine described in Japanese Patent Publication No. 59-1281, Japanese Patent Application Laid-Open No. 53-133428, and the like. Active halogen compounds, aromatic carbonyl compounds such as ketal, acetal, or benzoin alkyl ethers described in each specification such as US Patent No. 4318791, European Patent Publication EP88050A, and benzophenones described in US Patent No. 4199420 Aromatic ketone compounds, (thio) xanthones or acridine compounds described in French Patent-2456741, compounds such as coumarins or ropin dimers described in Japanese Patent Application Laid-open No. H10-62986, Japanese Patent Laid-Open No. 8-015521 And sulfonium organoboron complexes described in Japanese Patent Application Laid-Open Publication No. and the like.

Among them, acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, triazine series, halomethyloxadiazole series, acridine series, coumarins series, ropin dimer series, biimidazole series and the like desirable.

<Sensitizer>

The photosensitive composition of this invention may contain the sensitizer for the purpose of the improvement of the radical generation efficiency of a photoinitiator (radical initiator), and the long wavelength of a photosensitive wavelength. As a sensitizer which can be used for this invention, it is preferable to sensitize a radical initiator with an electron transfer mechanism or an energy transfer mechanism.

As a sensitizer which can be used for this invention, what belongs to the compounds listed below, and what has an absorption wavelength in the wavelength range of 300 nm-450 nm are mentioned.

Examples of preferred sensitizers include those belonging to the following compounds and those having an absorption wavelength in the 330 nm to 450 nm region.

For example, polynuclear aromatics (e.g. phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10- dialkoxy anthracene), xanthenes (e.g. fluorescein, eosin, erythrosine, rhodamine B, Rose Bengal), thioxanthones (isopropyl thioxanthone, diethyl thioxanthone, chlorothioxanthone), cyanines (e.g., thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), phthalocyanines, thiazines (e.g. thionine, methylene blue, toluidine blue), acridines (e.g. acridine orange, chloroflavin, arc Riflavin), anthraquinones (e.g. anthraquinones), squaryliums (e.g. squarialium), acridine orange, coumarins (e.g. 7-diethylamino-4-methylcoumarin) , Ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, Riphenylmethane, distyrylbenzenes, carbazoles, porphyrins, spiro compounds, quinacridones, indigo, styryls, pyrilium compounds, pyrromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid Aromatic ketone compounds, such as a derivative, a thiobarbituric acid derivative, acetophenone, benzophenone, a thioxanthone, Michler's ketone, heterocyclic compounds, such as N-aryl oxazolidinone, etc. are mentioned.

As for content of a sensitizer, the range of 0.1-30 mass% is preferable with respect to the mass of the total solid of a photosensitive composition from a viewpoint of a sensitivity and storage stability, The range of 1-20 mass% is more preferable, The 2-15 mass% of The range is more preferred.

It is also preferable that the photosensitive composition of this invention contains a sensitizer. In the present invention, the sensitizer has an action of further improving the sensitivity of the sensitizing dye and the initiator to the actinic radiation, or inhibiting the polymerization inhibition of the photopolymerizable compound by oxygen.

Examples of such a sensitizer include amines such as MR Sander et al., Journal of Polymer Society, Volume 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japan Japanese Patent Laid-Open No. 52-134692, Japanese Patent Laid-Open No. 59-138205, Japanese Patent Laid-Open No. 60-84305, Japanese Patent Laid-Open No. 62-18537, Japanese Patent Laid-Open No. 64-33104, Research The compound of Disclosure 33825, etc. are mentioned, Specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthio dimethylaniline, etc. are mentioned.

As another example of a sensitizer, thiols and sulfides such as thiol compounds disclosed in Japanese Patent Application Laid-Open No. 53-702, Japanese Patent Application Laid-Open No. 55-500806, Japanese Patent Application Laid-Open No. 5-142772, and Japanese Patent The disulfide compound of Unexamined-Japanese-Patent No. 56-75643, etc. are mentioned, Specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 (3H) -quinazoline, (beta) -mercaptonaphthalene, etc. are mentioned.

As another example, an amino acid compound (e.g., N-phenylglycine, etc.), an organometallic compound (e.g., tributyltin acetate, etc.) described in Japanese Patent Publication No. 48-42965, and Japanese Patent No. 55-34414 Hydrogen donors, sulfur compounds described in Japanese Patent Application Laid-Open No. 6-308727 (for example, trithiane, etc.);

As for content of a sensitizer, the range of 0.1-30 mass% is preferable with respect to the mass of the total solid of a photosensitive composition from a viewpoint of the hardening speed improvement by the balance of a polymerization growth rate and a chain transfer, and the range of 1-25 mass% is more Preferably, the range of 0.5-20 mass% is more preferable.

<Solvent>

Generally, the photosensitive composition of this invention can be preferably prepared using a solvent with the said component.

Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and lactic acid Methyl, ethyl lactate, methyl oxyacetic acid, ethyl oxyacetate, oxyacetic acid butyl, methoxyacetic acid methyl, methoxyacetic acid ethyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, and 3-oxypropionate methyl and 3-oxypropionic acid alkyl esters, such as 3-oxyethyl propionate (for example, 3-methoxy methyl propionate, 3-methoxy ethylpropionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate), and 2 To alkyl 2-oxypropionates such as methyl oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate. Ste (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2-methylpropionic acid Methyl, 2-oxy-2-methylpropionate, 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, Ethyl acetoacetic acid, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like;

Aromatic hydrocarbons such as toluene, xylene and the like.

Of these, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, acetic acid-n-butyl, 3-methoxypropionate methyl, 2-heptanone, cyclo Hexone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferable.

A solvent may be used independently and may be used in combination of 2 or more type.

<Other Ingredients>

The photosensitive composition of this invention contains various additives, such as a fluorine-type organic compound, a thermal polymerization inhibitor, a coloring agent, other fillers, polymeric compounds other than alkali-soluble resin, surfactant, adhesion promoter, antioxidant, a ultraviolet absorber, and anti-agglomeration agent as needed. can do.

<Fluorinated Organic Compound>

By containing a fluorine-type organic compound, the liquid characteristic (particularly fluidity) when it is set as a coating liquid can be improved, and the uniformity of coating thickness and liquid saving property can be improved. That is, since the interfacial tension between the substrate and the coating liquid is reduced, the wettability to the substrate is improved, and the coating property to the substrate is improved, so that even when a thin film having a thickness of several micrometers is formed with a small amount of liquid, the thickness of the uniform thickness is small. It is effective in that formation is possible.

3-40 mass% is preferable, as for the fluorine content rate of a fluorine-type organic compound, More preferably, it is 5-30 mass%, Especially preferably, it is 7-25 mass%. If the fluorine content is in the above range, it is effective in terms of coating thickness uniformity and liquid saving property, and solubility in the composition is also good.

As a fluorine-type organic compound, Megapack F171, copper F172, copper F173, copper F177, copper F141, copper F142, copper F143, copper F144, copper R30, copper F437 (above, DIC Corporation make), fluoride FC430 , East FC431, East FC171 (above, Sumitomo 3M Co., Ltd.), Supron S-382, East SC-101, East SC-103, East SC-104, East SC-105, East SC1068, East SC- 381, SC-383, S393, KH-40 (above, Asahi Glass Co., Ltd.), etc. are mentioned.

The fluorine-based organic compound is particularly effective for preventing application variation and thickness variation when the coating film to be formed, for example, is thinned. Moreover, it is effective also in slit application | coating which is easy to produce liquid breakage.

As for the addition amount of a fluorine-type organic compound, 0.001-2.0 mass% is preferable with respect to the total mass of a pigment dispersion composition or the photosensitive composition, More preferably, it is 0.005-1.0 mass%.

It is preferable to use the compound which has an epoxy ring as a thermal-polymerization component in order to raise the intensity | strength of the coating film formed for the photosensitive composition of this invention. Solvent resistance improves by using a compound which has an epoxy ring, or ITO sputtering aptitude is improved and it is preferable.

<Epoxy ring-containing compound>

As a compound which has an epoxy ring, the compound which has two or more epoxy rings in a molecule | numerator, such as a bisphenol A type, a cresol novolak type, a biphenyl type, and an alicyclic epoxy compound, is mentioned.

For example, as the bisphenol A compound, Efototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF- 170 etc (product made by Toto Kasei), Denacol EX-1101, EX-1102, EX-1103 (made by Kasei Nakase), Flaccel GL-61, GL-62, G101, G102 (product made by Daicel Kagaku) In addition, bisphenol F type and bisphenol S type similar to these are mentioned. Moreover, epoxy acrylates, such as Ebecryl 3700, 3701, 600 (made by Daicel Cytec), can also be used.

As a cresol novolak type compound, Efototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above Toto Kasei), Denacol EM-125, etc. (above Nagasase Kasei), As an alicyclic epoxy compound, such as 3,5,3 ', 5'- tetramethyl-4,4'- diglycidyl biphenyl as a biphenyl type compound, it is ceoxide 2021, 2081, 2083, 2085, eporide GT-301 , GT-302, GT-401, GT-403, EHPE-3150 (made by Daicel Kagaku), Santoto ST-3000, ST-4000, ST-5080, ST-5100 (made by Toto Kasei), Epiclon 430, 673, 695, 850S, 4032 (above DIC), etc. are mentioned.

1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o Phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and other glycidyl esters in which the backbone of an amine epoxy resin, efototo YH-434, YH-434L, and a bisphenol A epoxy resin, is modified with dimer acid. Etc. can also be used.

Among them, the "molecular weight / number of epoxy rings" is preferably 100 or more, more preferably 130 to 500. When the "molecular weight / number of epoxy rings" is small, the curability is high, the shrinkage upon curing is large, and when too large, the curability is insufficient, the reliability is poor, or the flatness is poor.

As a specific preferable epoxy ring containing compound, Efototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, FAXEL GL-61, GL-62, 3,5,3 ', 5'- Tetramethyl-4,4'- diglycidyl biphenyl, ceoxide 2021, 2081, eporide GT-302, GT-403, EHPE-3150, etc. are mentioned.

<Thermal polymerization initiator>

It is also effective to contain a thermal polymerization initiator in the photosensitive composition of the present invention. As a thermal polymerization initiator, various azo compounds and a peroxide compound are mentioned, for example. Examples of the azo compounds include azobis compounds, and examples of the peroxide compounds include ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester and peroxydicarbonate. Can be.

<Surfactant>

It is preferable to comprise using various surfactant for the photosensitive composition of this invention from a viewpoint of improving applicability | paintability, and various surfactant of nonionic, cationic, and anionic system can be used. Especially, the fluorine-type surfactant which has a perfluoroalkyl group as a nonionic surfactant is preferable.

As a specific example of a fluorine-type surfactant, the Megapack (registered trademark) series by DIC Corporation, the fluoride (registered trademark) series by 3M company, etc. are mentioned.

In addition to the above, specific examples of the additive include a filler such as glass and alumina; Itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, acid anhydride added to a polymer having a hydroxyl group, alcohol soluble nylon, bisphenol A and epichlorohydrin Alkali-soluble resins such as phenoxy resins; Surfactants such as nonionics, cationics and anionics, specifically phthalocyanine derivatives [commercially available EFKA-745 (manufactured by Morishita Sangyo Co., Ltd.)]; Organosiloxane polymer KP341 (manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.), (meth) acrylic acid-based (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyosisha Yushi Kagaku Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) Cationic surfactants such as;

Examples of the other additives include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol Distearate and sorbitan fatty acid esters (nonionic surfactants such as Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, etc. manufactured by BASF; Anionic surfactants such as W005, W017 (manufactured by Yusho Co., Ltd.), EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (more than Morishita Sangyo Co., Ltd.) Polymer dispersant; Solsper's dispersant (manufactured by Geneca), such as Solsper's 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121 , P-123 (manufactured by Asahi Denka Corporation) and Ionet S-20 (manufactured by Sanyo Kasei Co., Ltd.); 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, Ultraviolet absorbers such as alkoxybenzophenone, and anti-agglomerating agents such as sodium polyacrylate.

In addition, when promoting the alkali solubility of the uncured part and further improving the developability of the photosensitive composition, it is possible to add an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less, to the photosensitive composition. have. Specific examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sublinic acid, azelaic acid, sebacic acid, brazilian, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid and camphoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; And other carboxylic acids such as phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamildeacetic acid, kumaric acid and umbelic acid. Can be.

<Heat polymerization inhibitor>

It is preferable to add a thermal polymerization inhibitor to the photosensitive composition of the present invention, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzo Quinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzoimidazole, etc. This is useful.

The photosensitive composition of this invention contains alkali-soluble resin, a polymeric compound, and a photoinitiator (preferably with a solvent) in the pigment dispersion composition which disperse | distributed a pigment etc., and mixes additives, such as surfactant, as needed for this. It can prepare by making it.

[Color filter and its manufacturing method]

The color filter of this invention is produced by forming the colored film (coloring pattern) on board | substrates, such as glass, using the photosensitive composition of this invention mentioned above. For example, the photosensitive composition of the present invention is applied directly to a substrate or with another layer in between (preferably by a coating method such as rotation coating, slit coating, cast coating, roll coating, etc.) to form a photosensitive film, It is most preferable to form the coloring pattern (for example, colored pixel) of each color (for example, 3 color or 4 color) by exposing to the formed photosensitive film | membrane through a predetermined mask pattern, and developing and removing an uncured part with a developing solution after exposure. It is possible to produce a color filter.

For this reason, the color filter used for a liquid crystal display device or a solid-state image sensor can be manufactured with little process difficulty, high quality, and low cost.

At this time, as radiation used for exposure, especially ultraviolet rays, such as g line | wire, h line | wire, i line | wire, j line | wire, are preferable.

In the exposure method in the present invention, for example, an ultraviolet light laser can be used as the light source, but is not limited thereto. Laser is an acronym for Light Amplification by Stimulated Emission of Radiation in English. Oscillators and amplifiers that produce monochromatic light with greater coherence and directivity by amplifying and oscillating light waves by using the phenomenon of induced emission occurring in a material having an inversion distribution, crystals, glass, liquids, pigments, gases, etc. as excitation media From these media, lasers having an oscillation wavelength can be used for known ultraviolet light such as solid lasers, liquid lasers, gas lasers and semiconductor lasers. Especially, a solid state laser and a gas laser are preferable from a viewpoint of a laser output and an oscillation wavelength.

As a wavelength which can be used for this invention, the ultraviolet light laser of the wavelength range of 300 nm-380 nm is preferable, More preferably, the ultraviolet light laser of the wavelength of 300 nm-360 nm is matched with the photosensitive wavelength of a photosensitive film | membrane. It is preferable at the point.

Specifically, the third harmonic (355 nm) of the Nd: YAG laser of the solid laser having a large output and relatively low cost, and the XeCl (308 nm) and XeF (353 nm) of the excimer laser can be preferably used.

As exposure amount of a to-be-exposed object (pattern), it is the range of 1mJ / cm <2> -100mJ / cm <2>, and the range of 1mJ / cm <2> -50mJ / cm <2> is more preferable. It is preferable at the point of productivity of pattern formation that an exposure amount is this range.

In addition, it is preferable that the laser used for this invention is intermittently oscillated from a viewpoint of being easy to form a pattern in a desired position. The oscillation frequency of the intermittent oscillation pulse laser is preferably 20 to 2000 Hz, more preferably 30 to 1000 Hz. Oscillation at frequencies in this range can yield high productivity.

Although there is no restriction | limiting in particular as an exposure apparatus which can be used for this invention, As what is marketed, Callisto (made by V-Technology Co., Ltd.), EGIS (made by V-Technology Co., Ltd.), DF2200G (made by Dainippon Screen Co., Ltd.), etc. are used. It is possible. Moreover, the apparatus of that excepting the above can also be used preferably.

The ultraviolet light laser has good parallelism and can perform pattern exposure without using a mask at the time of exposure, but the pattern shape is affected by the shape and profile of the output light. Therefore, it is preferable to expose a pattern using a mask because the linearity of the pattern is increased.

Drying (prebaking) of the film by the photosensitive composition of the present invention applied to the substrate (preferably applied) can be carried out under a condition of 10 to 300 seconds in a temperature range of 50 to 140 ° C. using a hot plate or an oven. .

In image development, the uncured part after exposure is eluted to a developing solution, and only a hardened part remains. As image development temperature, it is 20-30 degreeC normally, and as image development time, it is 20 to 90 second.

As a developing solution, as long as it melt | dissolves the film | membrane of the photosensitive composition in an uncured part, as long as it does not melt a hardened part, any can be used. Specifically, a combination of various organic solvents and an alkaline aqueous solution can be used.

As said organic solvent, what was listed as the above-mentioned solvent which can be used when preparing the pigment dispersion composition or the photosensitive composition of this invention is mentioned.

As said alkaline aqueous solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl Alkaline compounds such as ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5.4.0] -7-undecene have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1 The alkaline aqueous solution melt | dissolved so that it may become mass% is mentioned.

In addition, when alkaline aqueous solution is used as a developing solution, washing | cleaning (rinse) with water is generally performed after image development.

After image development, excess developer is wash | cleaned and removed, and after drying, heat processing (post-baking) is generally performed at the temperature of 100-250 degreeC.

Post-baking is the heating after image development to make hardening perfect, and it heats (hard bake) of about 200 degreeC-250 degreeC normally. This post-baking process can be performed continuously or batchwise using heating means, such as a hotplate, a convection oven (hot air circulation type dryer), and a high frequency heater, so that the coating film after image development may become said condition.

By repeating the above operation sequentially for each color in accordance with the desired number of colors, a color filter in which a cured film in which a plurality of colors are colored is formed can be produced.

When providing the photosensitive composition of this invention on a board | substrate and forming a film, as a dry thickness of a film, it is generally 0.3-5.0 micrometers, Preferably it is 0.5-3.5 micrometers, Most preferably, it is 1.0-2.5 micrometers.

Examples of the substrate include alkali-free glass, soda glass, pyrex (registered trademark) glass, quartz glass, and a transparent conductive film attached thereto, and photoelectric conversion element substrates used in solid-state imaging devices and the like. Examples thereof include silicon substrates and plastic substrates. On these substrates, black stripes are usually formed to isolate each pixel.

It is preferable that the plastic substrate has a gas barrier layer and / or a solvent-resistant layer on its surface.

As another layer in the case of providing a photosensitive composition through another layer on a substrate, a gas barrier layer, a solvent-resistant layer, etc. are mentioned.

Although the photosensitive composition and the method of manufacturing a color filter of this invention can be used suitably for the color filter for liquid crystal display devices, it is not limited to this.

[Liquid crystal display device]

The liquid crystal display element of this invention comprises the color filter of this invention.

More specifically, the panel which is the liquid crystal display device of this invention is obtained by forming an oriented film in the inner surface side of the color filter of this invention, opposing an electrode substrate, and sealing a liquid crystal in a gap part.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. In addition, "%" "part" is a mass reference | standard unless there is particular notice.

[Examples 1-10, Comparative Examples 1-4]

[One. Preparation of colored photosensitive composition (A-1-A-14)]

As a photosensitive composition for color filter formation, the negative type coloring photosensitive composition (A-1) containing a coloring agent (pigment) was prepared, and the color filter was produced using this.

1-1. Preparation of Pigment Dispersion (P1)

40 parts by mass of a 30/70 (mass ratio) mixture of CI Pigment Green 36 and CI Pigment Yellow 219 as a pigment, 10 parts by mass of BYK2001 (Disperbyk: manufactured by BYK Corporation, 45.1 mass% of solids concentration) as a dispersant About 4.51 mass part) and the liquid mixture which consists of 150 mass parts of ethyl 3-ethoxy propionate as a solvent were mixed and disperse | distributed with the bead mill for 15 hours, and the pigment dispersion liquid P1 was prepared.

It was 200 nm as a result of measuring the average particle diameter of the pigment with respect to the obtained pigment dispersion liquid (P1) by the dynamic light scattering method.

1-2. Preparation of colored photosensitive composition (A-1-A-14) (coating liquid)

The components of the following composition were mixed and dissolved to prepare colored photosensitive compositions (A-1 to A-14).

<Composition (A-1 ~ A-14)>

600 parts by mass of pigment dispersion (P1)

150 parts by mass of alkali-soluble resin

(Benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, mol ratio: 80/10/10, Mw: 10000)

110 parts by mass of the polyfunctional monomer dipentaerythritol hexaacrylate

Oxime ester compound of Table 1 Mass part of Table 1

Solvent: 1000 parts by mass of propylene glycol monomethyl ether acetate

Surfactant (trade name: Tetranic 150R1, BASF) 1 part by mass

5 parts by mass of γ-methacryloxypropyltriethoxysilane

[2. Production of color filter]

2-1. Formation of Photosensitive Composition Layer

After using the coloring photosensitive composition (A-1) containing the pigment obtained by making it into a resist solution on the glass substrate of 550 mm x 650 mm on the following conditions, it slit-coated, it is maintained as it is for 10 minutes, and vacuum-dried and Prebaking (100 degreeC 80 second) was performed, and the photopolymerizable composition coating film (photosensitive composition layer) was formed.

(Slit application condition)

Gap of the opening of the dispensing head tip: 50 μm

Application speed: 100 mm / second

Clearance of substrate and coating head: 150㎛

Coating thickness (dry thickness): 2 μm

Application temperature: 23 ℃

2-2. Exposure, development

Then, the photosensitive composition layer was exposed in pattern shape using the 2.5 kW ultrahigh pressure mercury lamp. The entire surface of the photosensitive composition layer after exposure was developed for 60 seconds using 1.0% aqueous solution (25 ° C) of an inorganic developer (trade name: CDK-1, manufactured by Fujifilm Electronics, Inc.) at a shower pressure of 0.2 MPa. It washed with pure water.

2-3. Heat treatment

Thereafter, pure water was sprayed onto the photosensitive composition layer in a shower shape to wash away the developer, and then heated in an oven at 220 ° C. for 1 hour (postbaking).

Thereafter, a colored pattern is formed with a blue colored curable composition (CB-9500L: manufactured by FUJIFILM Electronics), and further, a red colored curable composition (CR-9500L: manufactured by FUJIFILM Materials) is manufactured. A coloring pattern was formed, ITO was vapor-deposited, the spacer was formed using the photocurable composition (CSP-3210L: Fujifilm Electronics Co., Ltd. product), and the color filter which has a coloring pattern on the board | substrate was obtained.

[3. Performance evaluation]

The storage stability and exposure sensitivity of a coloring photosensitive composition, the developability at the time of forming a coloring pattern on a glass substrate using a coloring photosensitive composition, the coloring by the time-lapse of the obtained coloring pattern, the board | substrate adhesiveness, and the pattern cross section shape It evaluated as follows. The evaluation results are collectively shown in Table 1.

3-1. About storage stability of a coloring photosensitive composition After storing a coloring photosensitive composition at room temperature for 1 month, the precipitation degree of a foreign material was evaluated visually according to the following criteria.

-Criteria-

(Circle): Precipitation was not confirmed.

(Triangle | delta): Precipitation was confirmed slightly.

X: Precipitation was confirmed

3-2. Exposure Sensitivity of Colored Photosensitive Composition

The coloring photosensitive composition was spin-coated on a glass substrate, and then dried to form a coating film having a film thickness of 1.0 μm. Spin coating conditions were 5 seconds at 300 rpm, and 20 seconds at 800 rpm, and drying conditions were 80 seconds at 100 degreeC. Subsequently, the obtained coating film was exposed at various exposure doses of 10 mJ / cm <2> -1600 mJ / cm <2> by the proximity type exposure machine (made by Hitachi Hi-Tech Denshi Engineering Co., Ltd.) with an ultrahigh pressure mercury lamp using the test photomask of 2.0 micrometers of line widths. Subsequently, the coating film after exposure was developed on 25 degreeC and the conditions for 60 second using CDK-1 (made by Fujifilm Electronics) Ltd. diluted to 1%. Thereafter, the mixture was rinsed with running water for 20 seconds, and then spray-dried to complete patterning.

Evaluation of exposure sensitivity evaluated the minimum exposure amount whose film thickness after image development of the area | region to which light was irradiated in the exposure process was 95% or more with respect to 100% of the film thickness before exposure as an exposure required amount. The smaller the value of the required exposure amount, the higher the sensitivity.

3-3. Developability, coloring by time of heating, pattern cross-sectional shape, substrate adhesion

`` 2-3. Heat treatment ”, and evaluated the developability, board | substrate adhesiveness, and pattern cross-sectional shape by confirming the board | substrate surface and cross-sectional shape after post-baking by a conventional method by optical microscope and SEM photograph observation. The detail of an evaluation method is as follows. The results are shown in Table 1.

<Developing>

In the exposure process, the presence or absence of the residue of the area | region (unexposed part) which was not irradiated with light was observed, and developability was evaluated. Evaluation criteria are as follows.

-Evaluation standard-

(Circle): No residue was confirmed by the unexposed part.

(Triangle | delta): Although the residue was confirmed slightly in an unexposed part, it was a degree which is satisfactory practically.

X: The residue was remarkably confirmed by an unexposed part.

<Substrate adhesiveness>

Substrate adhesiveness was evaluated based on the following criteria by observing whether or not a pattern defect had occurred.

-Evaluation standard-

(Circle): A pattern defect was not observed at all.

(Triangle | delta): A pattern defect was hardly observed but a partial defect was observed.

X: Remarkably many pattern defects were observed.

<Pattern cross-sectional shape>

The cross-sectional shape of the formed pattern was observed and evaluated. As for the cross-sectional shape of a pattern, pure taper is the most preferable, and rectangle is next. Reverse taper is undesirable.

<Color evaluation by forced heating time>

The photosensitive composition layer (coloring pattern) after exposure and development was heated on a hot plate at 200 ° C. for 1 hour, and the color difference (ΔEab ^* ) before and after heating was evaluated by Otsuka Denshi Co., Ltd. MCPD-3000 based on the following criteria. did.

-Evaluation standard-

○: ΔEab ^* ≤ 5

Δ: 5 <ΔEab ^* <8

×: ΔEab ^* ≥ 8

[Examples 11-16, Comparative Examples 5-7]

In the composition (A-1) used for the preparation of the colored photosensitive composition (A-1) in Example 1, 30 parts by mass of the oxime ester compound (I-1) was changed to the oxime ester compound and the base amount shown in Table 2 below. , Except that the sensitizer and / or sensitizer were added in the kind and amount shown in Table 2 below, all were prepared in the same manner as in Example 1 to prepare colored photosensitive compositions (B-1 to B-9) to obtain a color filter. . Moreover, evaluation similar to Example 1 was performed. The results are shown in Table 2.

[Examples 17-25, Comparative Examples 8-10]

Synthesis of halogenated zinc phthalocyanine pigment

Zinc phthalocyanine was manufactured using phthalodinitrile and zinc chloride as a raw material.

Halogenation was performed by mixing 3.1 parts of sulfuryl chloride, 3.7 parts of anhydrous aluminum chloride, 0.46 parts of sodium chloride, and 1 part of zinc phthalocyanine at 40 ° C, and adding 2.2 parts of bromine dropwise. The mixture was reacted at 80 DEG C for 15 hours, after which the reaction mixture was poured into water to precipitate a partially zinc bromide phthalocyanine crude pigment. This aqueous slurry was filtered, 80 degreeC warm water washing was performed, and it dried at 90 degreeC, and 2.6 parts of refined partial zinc bromide phthalocyanine crude pigments were obtained.

1 part of this partial zinc bromide phthalocyanine crude pigment, 7 parts of crushed sodium chloride, 1.6 parts of diethylene glycol, and 0.09 parts of xylene were placed in a twin kneader and kneaded at 100 ° C for 6 hours. After kneading, the mixture was extracted with 100 parts of water at 80 ° C., stirred for 1 hour, and then filtered, hot washed, dried, and ground to obtain a partially zinc bromide phthalocyanine pigment.

The obtained partial zinc bromide phthalocyanine pigment was ZnPcBr ₁₀ Cl ₄ H ₂ (Pc; phthalocyanine) from the halogen content analysis by mass spectrometry, and contained 10 bromine on average in 1 molecule.

In addition, the average value of the primary particle diameter measured with the transmission electron microscope (JEM-2010 by Nippon Denshi Co., Ltd.) was 0.065 micrometer.

Synthesis Example 1 Synthesis of Resin (i-1)

6.4 g of n-octanoic acid, 200 g of epsilon -caprolactone, and 5 g of titanium (IV) tetrabutoxide were mixed and heated at 160 ° C for 8 hours, and then cooled to room temperature to obtain a polyester resin (i-1).

The scheme is shown below.

Synthesis Example 2 Synthesis of Resin (J-1)

10 g of polyethyleneimine (SP-018, number average molecular weight 1,800, manufactured by Nippon Shokubai) and 100 g of polyester resin (i-1) were mixed, and heated at 120 ° C. for 3 hours to obtain an intermediate (J-1B). Thereafter, the mixture was allowed to cool to 65 ° C, and 200 g of propylene glycol 1-monomethyl ether 2-acetate (hereinafter referred to as PGMEA) containing 3.8 g of succinic anhydride was slowly added thereto, followed by stirring for 2 hours. Then, PGMEA was added and the 10 mass% solution of PGMEA of resin (J-1) was obtained. Resin (J-1) has a side chain derived from polyester (i-1) and a carboxyl group derived from succinic anhydride.

The synthetic scheme is shown below.

Preparation of dispersion of green pigment zinc halide phthalocyanine

14.9 parts of partial zinc bromide phthalocyanine pigments (referred to as PG58) obtained above in the high-speed disperser "TSC-6H" made by Igarashi Kikai Seijo Co., Ltd. made with zirconia beads of diameter 0.5mm, 7.2 parts of acrylic dispersants "BYK-2001" made by Big Chem Corporation, 78 parts of PGMEAs were added, and it stirred for 8 hours at 2000 revolutions per minute, and prepared the dispersion liquid of the partially brominated zinc-halide phthalocyanine pigment (PG58).

Preparation of Dispersion of Yellow Pigment (PY150)-

40 parts (average particle diameter 60nm) of CI pigment yellow 150 (PY150) as a pigment, the bead mill (zirconia beads) 223 parts (22.3 parts by solid content conversion) of the PGMEA 10 mass% solution of the said resin (J-1) 0.3 mm) was mixed and dispersed for 3 hours to prepare a pigment dispersion.

The coloring photosensitive composition was prepared with the following composition.

(Composition (C-1 ~ C-12))

26.1 parts of dispersion of green pigment (PG58)

14.3 parts of a dispersion of yellow pigment (PY150)

2.8 parts of binder resin (benzyl methacrylate-acrylic acid (= copolymerization molar ratio 6: 4) copolymer, weight average molecular weight 9000)

3.58 parts of monomers (7: 3 (mass ratio) mixture of Nippon Kayaku Co., Ltd. brand name: KAYARAD DPHA, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate)

1.02 part of the oxime ester compound of Table 3

Compound having an epoxy ring (2,2-bis (hydroxymethyl = 1-butanol 1,2-epoxy-4- (2-oxolanyl) cyclohexane adduct, EHPE-3150 manufactured by Daicel Kagaku Corporation) 0.480 parts

Polymerization inhibitor (p-methoxyphenol) 0.0018 parts

Surfactant (Fluorinated surfactant, DIC Corporation brand name Megapack F781-F)

                                                              0.0334parts

0.320 parts of silane coupling agent (3-methacryloyloxy-trimethoxysilylpropane)

Solvent (PGMEA) 51.42 parts

Other than that was carried out similarly to Example 1, and the color filter was obtained. Moreover, evaluation similar to Example 1 was performed. The results are shown in Table 3.

The oxime ester compound in Tables 1-3 is each compound mentioned above as an exemplary compound of a specific oxime ester compound.

In addition, the detail and structural formula of the comparative compound 1-the comparative compound 4, the sensitizer S1-the sensitizer S3, and the sensitizer 1-the sensitizer 2 are shown below.

Comparative compound 1: IRGACURE OXE01 (made by Chiba specialty chemicals company)

Comparative Compound 2: IRGACURE 907 (manufactured by Chiba Specialty Chemicals Co., Ltd.)

Comparative Compound 3: IRGACURE 369 (manufactured by Chiba Specialty Chemicals Co., Ltd.)

Sensitizer S1: 4, 4-bisdiethylamino benzophenone

Sensitizer S2: Diethyl Thioxanthone

Notary sensitizer 1: 2-mercaptobenzothiazole

Co-sensitizer 2: N-phenyl-2-mercaptobenzoimidazole

As can be seen from the results of Tables 1 to 3, the photosensitive composition of the example using the specific oxime ester compound has a high sensitivity, is excellent in storage stability, and a cured film capable of suppressing coloring due to heat and aging is obtained. It can be seen that. Moreover, it turns out that the color filter formed using the said photosensitive composition has a favorable pattern cross-sectional shape, and is excellent in adhesiveness with a support body.

The photosensitive composition using a specific oxime ester compound can achieve sufficient sensitivity even if a laser is used as an exposure source, and can also reduce the coloring at the time of heating. Examples of the photosensitive composition for laser exposure are shown below.

(Synthesis example of binder resin used for photosensitive composition for laser exposure: Synthesis of allyl methacrylate / methacrylic acid copolymer (molar ratio = 80/20))

54 g of 1-methoxy-2-propanol was placed in a 200 ml three-necked flask equipped with a stirring rod equipped with a stirring blade, a reflux cooling tube, and a thermometer, and heated to 70 ° C. under a nitrogen stream. 10.07 g of allyl methacrylate, 1.93 g of methacrylic acid, and 0.185 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator were dissolved in 54 g of 1-methoxy-2-propanol as a plunger. It dripped in the three neck flask over 2.5 hours using the pump. After completion of the dropwise addition, the mixture was further stirred at 70 ° C for 2 hours. After the completion of heating, the mixture was poured into 1 liter of water and reprecipitated. The precipitate was filtered and dried in vacuo to obtain 9 g (yield 75%) of polymer compound (B-1).

0.01 g of the measurement sample of the weight average molecular weight was etched in a 10 ml volumetric flask, and about 8 ml of THF was added and dissolved at room temperature, and the total amount was 10 ml. The weight average molecular weight of the polymer compound (B-1) was 35000 when the solution was measured under the following conditions using GPC.

(Synthesis of resin used for the photosensitive composition for laser exposure)

Synthesis Example Synthesis of Polymer 1

27.0 parts of monomer 1 (following structure), 126.0 parts of methyl methacrylate, 27.0 parts of methacrylic acid, and 420.0 parts of 1-methoxy-2-propanol were introduced into a three-necked flask with nitrogen substitution, followed by a stirrer (Shinto Kagaku Co., Ltd.). : It was stirred with a three-one motor, heated while flowing nitrogen in a flask, and it heated up to 90 degreeC. 1.69 parts of 2, 2- azobis (2, 4- dimethylvaleronitrile) (V-65 by Wako Pure Chemical Industries, Ltd.) was added here, and it heated and stirred at 90 degreeC for 2 hours. After 2 hours, 1.69 parts of V-65 was further added, followed by heating and stirring for 3 hours to obtain a 30 mass% solution of Polymer 1. It was 2.00,000 when the weight average molecular weight of the obtained polymer 1 was measured by the gel permeation chromatography method (GPC) which made polystyrene the reference material. In addition, the acid value per solid content was 98 mgKOH / g from the titration using sodium hydroxide.

Synthesis Example Synthesis of Polymer 2

27.0 parts of monomer 2 (following structure), 126.0 parts of methyl methacrylate, 27.0 parts of methacrylic acid, and 420.0 parts of 1-methoxy-2-propanol were introduced into a three-necked flask with nitrogen substitution, and then agitated (Shinto Kagaku Co., Ltd.). : It was stirred with a three-one motor, heated while flowing nitrogen in a flask, and it heated up to 90 degreeC. 1.80 parts of 2, 2- azobis (2, 4- dimethylvaleronitrile) (V-65 by Wako Pure Chemical Industries, Ltd.) was added here, and it heated and stirred at 90 degreeC for 2 hours. After 2 hours, 1.80 parts of V-65 was further added, followed by heating and stirring for 3 hours to obtain a 30% by mass solution of Polymer 2. It was 2.10,000 when the weight average molecular weight of Polymer 2 obtained by the gel permeation chromatography method (GPC) which made polystyrene the reference material was measured. In addition, the acid value per solid content was 99 mgKOH / g from the titration using sodium hydroxide.

The detail is shown about the coating pigments 1-6 used in order to prepare the pigment dispersion liquids 1-5 used for the Example and comparative example of the photosensitive composition for laser exposure.

(Preparation of Coating Pigment 1)

50 parts of pigment (CI Pigment Red 254 CROMOPHTAL RED BP manufactured by Chiba Specialty Chemicals), 500 parts of sodium chloride, 20 parts of the solution of the polymer 1, and 100 parts of diethylene glycol were placed in a stainless steel gallon kneader (manufactured by Inoue Seisakusho), 9 Time was kneaded. Subsequently, this mixture was poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and a solvent, and dried to prepare Coating Pigment 1.

(Preparation of Coating Pigment 2)

In the preparation of the coating pigment 1, C. I. Pigment Red 177 (CROMOPHTAL RED A2B manufactured by Chiba Specialty Chemicals) was used instead of Pigment Red 254, and the other coating agent 2 was prepared in the same manner as the preparation of the coating pigment 1.

(Preparation of Coating Pigment 3)

In the preparation of the coating pigment 1, CI Pigment Green 36 (Monastral Green 6Y-CL from Nippon Lubrizol Corporation) is used instead of Pigment Red 254, and polymer 2 is used instead of polymer 1, and the other is the same as the preparation of coating pigment 1 To coat pigment 3 was prepared.

(Preparation of Coating Pigment 4)

In the preparation of the coating pigment 1, C. I. Pigment Blue 15: 6 was used instead of Pigment Red 254, and the other coating pigment 4 was prepared like the preparation of the coating pigment 1.

(Preparation of Coating Pigment 5)

In the preparation of the coating pigment 1, Yellow Pigment E4GN-GT (manufactured by LANXESS) was used instead of Pigment Red 254, and polymer 2 was used instead of the polymer 1, and others were prepared in the same manner as the preparation of the coating pigment 1 to prepare the coating pigment 5 did.

(Preparation of Coating Pigment 6)

In the preparation of the coating pigment 1, C. I. pigment violet 23 was used instead of Pigment Red 254, and the other coating coating 6 was prepared like the preparation of the coating pigment 1.

The pigment dispersion liquids 1-7 used for the Example and the comparative example are shown in detail.

(Adjustment of Pigment Dispersion 1)

With respect to 35 parts of the pigment equivalent of the coating pigment 1, 14 parts of DisperBYK161 (manufactured by BYK-CHEMIE) as a dispersant and a solvent: 200 parts of propylene glycol monomethyl ether acetate were stirred at a rotational speed of 3,000 rpm for 3 hours using a homogenizer. The mixture was mixed to prepare a mixed solution, and further, dispersion treatment was performed for 6 hours using a bead disperser ultra apex mill (manufactured by Kotobuki Kogyo Co., Ltd.) using 0.1 mm zirconia beads.

(Adjustment of Pigment Dispersion 2)

In the preparation of the pigment dispersion 1, the coating pigment 2 was used instead of the coating pigment 1, and the others were prepared in the same manner as the preparation of the pigment dispersion 1 to prepare the pigment dispersion 2.

(Adjustment of Pigment Dispersion 3)

In the preparation of the pigment dispersion 1, the coating pigment 3 was used instead of the coating pigment 1, and the others were prepared in the same manner as the preparation of the pigment dispersion 1 to prepare the pigment dispersion 3.

(Adjustment of Pigment Dispersion 4)

In the preparation of the pigment dispersion 1, the coating pigment 5 was used instead of the coating pigment 1, and the others were prepared in the same manner as the preparation of the pigment dispersion 1 to prepare the pigment dispersion 4.

(Adjustment of Pigment Dispersion 5)

In the preparation of the pigment dispersion 1, the coating pigment 4 and the coating pigment 6 instead of the coating pigment 1 is a mass ratio of the coating pigment 4 / coating pigment 6 = 100/40, the total amount of the coating pigment 1 in the preparation of the pigment dispersion 1 and It used so that it may be the same amount, and the other thing was prepared similarly to the preparation of the pigment dispersion 1, and the pigment dispersion 5 was prepared.

(A) polymeric compound, (B) binder resin, and epoxy compound which were used for the Example and the comparative example are as follows.

(A) Polymerizable Compound:

(A-1) KAYARAD DPHA (made by Nippon Kayaku Co., Ltd., ethylenically unsaturated compound)

(B) binder resin:

(B-1) Allyl methacrylate / methacrylic acid copolymer (molar ratio = 80/20) solid content 100wt%

Epoxy Compounds:

(E-1) EHPE3150 (product made by Daicel Kagaku Kogyo Co., Ltd.)

(Example 26)

(Preparation of photosensitive composition CB-1)

The components of the following compositions were stirred and mixed to prepare blue photosensitive composition CB-1.

Ethylenic unsaturated compound: 4.4 parts (A-1)

Binder Resin: (B-1) 3.9 parts

Coloring agent: pigment dispersion 5 14.6 parts

Oxime ester compound: (I-1) 3.4 parts

Epoxy compound: (E-1) 0.5 part

Solvent: Propylene glycol methyl ether acetate 73 parts

Polymerization inhibitor: 0.002 parts of p-methoxyphenol

Surfactant: 0.007 parts Mega Pack F781F (DIC Corporation)

(Formation of the pixel)

After applying CB-1 onto the surface of an alkali-free glass substrate (Corning, 1737, 550 mm x 660 mm) using a slit coater (Hirata Kikou Co., Ltd., HC-6000), clean at 90 ° C. Prebaking was performed for 120 second in the oven, and the coating film of 1.7 micrometers in thickness was formed.

Subsequently, using EGIS (V Technology Co., Ltd., 3rd harmonic wavelength 355 nm, pulse width 6 nsec) as a laser exposure apparatus, the pulse irradiation of about 1mJ / cm <2> is performed 20 times, and the photo | photography to the photosensitive composition layer surface. Done through a mask. Subsequently, this substrate was prepared by using a developing apparatus (manufactured by Hitachi High Technology Co., Ltd.) with 1.0% developer (1 part by mass of CDK-1, pure water) of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Materials). 99 mass parts diluted liquid, 25 degreeC), shower pressure was set to 0.20 Mpa, it developed for 50 second, and it air-dried after washing | cleaning with pure water. Thereafter, 30 minutes post-bake was performed in the clean oven at 220 degreeC, and the blue stripe pixel array was formed on the board | substrate.

(Examples 27 and 28, Comparative Example 11)

(Preparation of photosensitive composition CB-2-4)

In the photosensitive composition used in Example 26, blue photosensitive compositions CB-2 to 4 were prepared in the same manner as in CB-1 prepared in Example 26, except that the oxime ester compound or the comparative compound was changed as shown in Table 4. did.

(Formation of the pixel)

A blue stripe pixel array was formed on a substrate in the same manner as in Example 26, using CB-2 to 4 instead of CB-1 used in Example 26.

(Example 29)

(Preparation of photosensitive composition CR-1)

The components of the following compositions were stirred and mixed to prepare red photosensitive composition CR-1.

Ethylenic unsaturated compound: (2.9 parts) 2.9 parts

Binder Resin: (B-1) 1.2 parts

Colorant: pigment dispersion 1 15.4 parts

Coloring agent: pigment dispersion 2 13.8 parts

Coloring agent: pigment dispersion 4 6.6 parts

1.6 parts of oxime ester compound I-1

Epoxy compound: (E-1) 0.5 part

Solvent: 58 parts of propylene glycol methyl ether acetate

Polymerization inhibitor: 0.002 parts of p-methoxyphenol

Surfactant: 0.007 parts Mega Pack F781F (DIC Corporation)

(Formation of the pixel)

By using CR-1 instead of CB-1 used in Example 26, a red stripe pixel array was formed on a substrate in the same manner as in Example 26.

(Example 30)

(Preparation of photosensitive composition CG-1)

The components of the following compositions were stirred and mixed to prepare green photosensitive composition CG-1.

Ethylenic unsaturated compound: 3.2 parts (A-1)

Binder Resin: (B-1) 1.5 parts

Coloring agent: pigment dispersion 3 20.6 parts

Coloring agent: pigment dispersion 4 11.4 parts

2.4 parts of oxime ester compound I-1

Epoxy compound: (E-1) 0.5 part

Solvent: 60 parts of propylene glycol methyl ether acetate

Polymerization inhibitor: 0.002 parts of p-methoxyphenol

Surfactant: 0.007 parts Mega Pack F781F (DIC Corporation)

(Formation of the pixel)

By using CG-1 instead of CB-1 used in Example 26, a green stripe pixel array was formed on a substrate in the same manner as in Example 26.

(Preservation stability)

After storing the photosensitive composition for 1 month at room temperature, the degree of precipitation of the foreign matter was visually evaluated according to the following criteria.

-Criteria-

(Circle): Precipitation was not confirmed.

(Triangle | delta): Precipitation was confirmed slightly.

X: Precipitation was confirmed

(Evaluation of surface roughness)

Each surface roughness was measured using AFM (Dimension3100, Veeco Instruments). The measurement area was 10 micrometer square.

Evaluation of surface roughness was performed as follows.

◎: 6 nm or less

○: greater than 6 nm ~ 8 nm or less

△: greater than 8 nm-10 nm or less

X: larger than 10 nm

(Evaluation of Line Width Stability)

The formed pixel pattern was observed by the field emission scanning electron microscope S-4800 (made by HITACHI), and line width stability was evaluated.

(Double-circle): The unevenness | corrugation of the end of a pattern is 0.3 micrometer or less, and line width is stable.

(Circle): The unevenness | corrugation of the end of a pattern is larger than 0.3 micrometer, and is 0.8 micrometer or less, and line width is substantially stable.

(Triangle | delta): The unevenness | corrugation of the end of a pattern is larger than 0.8 micrometer, and is 1.5 micrometer or less, and line width is somewhat unstable.

×: Stable pattern cannot be formed

(Evaluation of heat resistance)

The board | substrate with a pixel was further baked for 60 minutes in the 220 degreeC clean oven, and color change ((DELTA) E * ab) before and after further baking was evaluated using the Otsuka Denshi Corporation spectrophotometer MCPD-2000. Here, ΔE * ab means the color difference in the L * a * b * color system. It evaluated by the change ((DELTA) E * ab) value of a color difference.

◎: 1.5 or less

○: greater than 1.5 ~ 2.5 or less

△: greater than 2.5 ~ 3.5 or less

×: greater than 3.5

Table 4 shows the evaluation results of the storage stability, surface roughness, line width stability, and heat resistance of Examples 26 to 30 and Comparative Example 11.

From the results in Table 4, it can be seen that the pixel (coloring pattern) formed by exposing the photosensitive composition of the present invention by an ultraviolet light laser has very good pattern shape and line width stability, and the color change by the heat resistance test is small. .

Moreover, it turns out that the surface for RGB colored pixels which is the photosensitive composition layer produced with the photosensitive composition of this invention is very smooth.

In addition, by producing the photosensitive composition of the present invention, the line width stability of the pattern is increased, and even in the case of using a small mask and exposing using a laser without a mask, a margin of manufacture can be generated and productivity can be expected to be improved. In contrast, it can be seen that the comparative example lacking the constitution of the photosensitive composition of the present invention is unsuitable in the exposure method using a laser because the surface roughness is large and the line width stability of the pattern is inferior.

Moreover, when the liquid crystal display device was comprised using the color filter created by the Example and the comparative example, respectively, the light leakage in the dark place of the Example was few and the image quality improved.

Further, even when the photosensitive compositions of Examples 26 to 30 were exposed in a pattern shape using a 2.5 kW ultra-high pressure mercury lamp, a color filter pattern showing surface roughness, line width stability, and heat resistance equivalent to that of laser exposure at an exposure dose of 40 mJ / cm 2 was obtained. Obtained.

Claims (14)

The photosensitive composition containing (A) polymeric compound, (B) binder resin, and (C) photoinitiator represented by following General formula (1).

[In Formula (1), R and B each independently represents a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and Y represents an oxygen atom or a carbonyl group.] The photosensitive composition according to claim 1, wherein B in General Formula (1) is a monovalent substituent selected from the group consisting of the following Structural Formulas (2) to (5).

[In Structural Formula (2), X each independently represents a monovalent substituent, and Z represents an alkyl or phenyl group having 1 to 5 carbon atoms. n is an integer of 0-5.] The photosensitive composition of Claim 1 whose content of the photoinitiator represented by said (C) following General formula (1) is 0.1-40 mass parts with respect to 100 mass parts of total solids of the said photosensitive composition. The photosensitive composition according to claim 1, further comprising (D) a pigment. The photosensitive composition as claimed in claim 4, further comprising (E) a pigment dispersant. The photosensitive composition according to claim 4, which is used for formation of a colored region of a color filter. The photosensitive composition according to claim 5, which is used for formation of a colored region of a color filter. 7. The photosensitive composition as claimed in claim 6, wherein formation of the colored region of the color filter is performed using an ultraviolet light laser having a wavelength of 300 nm to 380 nm as an exposure source. 8. The photosensitive composition as claimed in claim 7, wherein the colored region of the color filter is formed using an ultraviolet light laser having a wavelength of 300 nm to 380 nm as an exposure source. It has a colored region formed on the base material using the photosensitive composition of Claim 6, The color filter characterized by the above-mentioned. It has a colored region formed on the base material using the photosensitive composition of Claim 7, The color filter characterized by the above-mentioned. It has a colored region formed on the base material using the photosensitive composition of Claim 8, The color filter characterized by the above-mentioned. It has a colored region formed on the base material using the photosensitive composition of Claim 9, The color filter characterized by the above-mentioned. The liquid crystal display device provided with the color filter in any one of Claims 9-13.