JP2008076807A - Photosensitive colored composition and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive colored composition having high sensitivity and giving an excellent pattern profile even in the case of a high dye content or a large film thickness and a color filter using the same. <P>SOLUTION: The photosensitive colored composition comprises a dye carrier comprising a transparent resin or a precursor thereof, a dye and a photopolymerization initiator represented by general formula (1). The color filter has a filter segment or a black matrix formed from the photosensitive colored composition on a transparent substrate. In formula, A and B each independently represent a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed polycyclic hydrocarbon group; and X represents a monovalent organic residue. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photosensitive coloring composition, and in particular, for color filters used in liquid crystal display devices and solid-state image sensors, formation of color filter segments such as red, green, blue, yellow, orange, cyan, and magenta, and a black matrix. It is related with the highly sensitive photosensitive coloring composition useful for. The present invention also relates to a color filter formed using the photosensitive coloring composition.

A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.
Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to form them generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher.

For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.
In the case of the pigment dispersion method, a photosensitive coloring composition (pigment resist) in which a pigment is dispersed in a photosensitive transparent resin solution is applied to a transparent substrate such as glass, and the solvent is removed by drying. After exposure, the unexposed areas are removed in the development process to form a pattern for the first color, and after processing such as heating as necessary, the same operation is sequentially repeated for all filter colors. Can be manufactured.

In recent years, color liquid crystal display devices have formed a large market for liquid crystal color televisions, car navigation and liquid crystal display integrated laptops, and monitors and televisions for desktop computers that take advantage of energy and space saving features. As it has begun to spread. Although attention is paid to a display device that replaces a conventional CRT, the color reproduction characteristic of a liquid crystal display device is inferior to that of a CRT at present.
Therefore, there is an increasing demand for high color reproducibility in color filters in which filter segments for each color are arranged.

  In order to improve contrast, a black matrix is generally arranged between the filter segments of each color of the color filter. However, the material for forming this black matrix has recently become an environmental problem, low reflection, and low cost. In view of the above, attention is focused on a resin black matrix in which a light-shielding pigment is dispersed in a resin instead of a metal chromium black matrix. However, the resin black matrix has a problem that the light shielding property (optical density) is lower than that of the metal chromium black matrix.

In order to improve the color reproduction characteristics of the color filter and to improve the light shielding property of the black matrix, it is necessary to increase the content of the dye in the photosensitive coloring composition or to increase the film thickness. However, in the method of increasing the content of the dye, problems such as a decrease in sensitivity, developability and resolution are generated. In the method of increasing the film thickness, there is a problem that the exposure light does not reach the bottom of the film and the pattern shape becomes defective.
In order to solve such a problem, it is necessary to increase the sensitivity of the photosensitive coloring composition. Generally, (1) imparting a reactive double bond to the resin, (2) a photopolymerization initiator, A sensitizer is selected or increased, and (3) a monomer is selected or increased.
JP 2001-233842 A JP 2001-264530 A JP 2003-156842 A

However, improvement in sensitivity is limited only by the addition of a double bond to the resin and the selection of a photopolymerization initiator, a sensitizer, and a monomer. In particular, when the amount of the photopolymerization initiator is increased, coloring due to a color unique to the photopolymerization initiator, a decrease in heat resistance, a decrease in light transmittance, a decrease in resolution, and the like occur. Further, when the amount of the monomer is increased, problems such as tackiness occur.
Accordingly, an object of the present invention is to provide a photosensitive coloring composition having high sensitivity and excellent pattern shape even when the pigment content is high or the film thickness is large, and a color filter using the same. .

The photosensitive coloring composition of the present invention is characterized by using a photopolymerization initiator represented by the following general formula (1) in order to obtain a high sensitivity and an excellent pattern shape. To do.
That is, the photosensitive coloring composition of the present invention is a photosensitive coloring composition containing a transparent resin and a dye carrier composed of a precursor thereof, a dye, and a photopolymerization initiator represented by the following general formula (1).
Moreover, the color filter of this invention is a color filter which comprises the filter segment formed from the said photosensitive coloring composition.
Moreover, the color filter of this invention is a color filter which comprises the black matrix formed from the said photosensitive coloring composition.

（式中、ＡおよびＢは、それぞれ独立に、置換もしくは未置換の複素環基または置換もしくは未置換の縮合多環炭化水素基を表し、Ｘは一価の有機残基を表す。） General formula (1)

(In the formula, A and B each independently represent a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed polycyclic hydrocarbon group, and X represents a monovalent organic residue.)

The photosensitive coloring composition of the present invention is highly sensitive and excellent even when the pigment content is high or the formed film thickness of each color filter segment and black matrix is large by using a specific compound as a photopolymerization initiator. Each color filter segment and black matrix pattern can be formed.
Therefore, a high quality color filter can be obtained by using the photosensitive coloring composition of the present invention.

First, the photosensitive coloring composition in this invention is demonstrated concretely.
The photosensitive coloring composition of this invention contains the photoinitiator represented by the pigment | dye carrier which consists of transparent resin and its precursor, a pigment | dye, and the said General formula (1). The photopolymerization initiator represented by the general formula (1) has high sensitivity, and an excellent pattern-shaped filter segment and black matrix can be obtained by using a photosensitive coloring composition containing the photopolymerization initiator. Can be formed.

The photopolymerization initiator represented by the general formula (1) has an α, α′-diketooxime ester having a heterocyclic group or a condensed polycyclic hydrocarbon group at the 1-position and the 3-position. A compound. By introducing a heterocyclic group or a condensed polycyclic hydrocarbon group into A and B, an absorption band is provided from the near ultraviolet to the visible region, and activity is provided from the near ultraviolet to the longer wavelength region than visible. And active radicals can be efficiently generated by irradiation with energy rays, particularly light.
In general formula (1), A and B each independently represent a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted condensed polycyclic hydrocarbon group.

  Examples of the heterocyclic group in the substituted or unsubstituted heterocyclic group in the general formula (1) include aromatic or aliphatic heterocyclic groups containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Examples include 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, iso Benzofuranyl group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H -Indolyl group, 2-indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidine Group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridine Group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, Pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thiol Xanthryl group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathinyl group, 3-coumarinyl group, dibenzofuranyl group, coumaranyl group, 2-thiocoumarinyl group, xanthonyl group, dibenzothienyl Groups, thioxanthenyl groups, oxazolyl groups, benzoxazolyl groups, benzothiazolyl groups, 1,4-dithianaphthyl groups, and the like, but are not limited thereto. In addition, the substituted or unsubstituted heterocyclic group may be bonded to the carbon atom of the general formula (1) at a substitution position other than the above, as long as the substitution position can form a covalent bond with the carbon atom. There is no particular limitation.

  As the condensed polycyclic hydrocarbon group in the substituted or unsubstituted condensed polycyclic hydrocarbon group in the general formula (1), a condensed polycyclic hydrocarbon group in which a ring structure is formed of 7 or more carbon atoms is used. Specific examples include indenyl group, 1,3-indandionyl group, naphthyl group, β-tetralonyl group, α-naphthoquinolyl group, pentarenyl group, azulenyl group, heptalenyl group, fluorenyl group, fluorenonyl group, anthryl group, 9 (10H) -anthracenonyl group, anthracenequinonyl group, anthraquinonyl group, phenanthryl group, 9,10-phenanthrenequinonyl group, biphenylenyl group, s-indacenyl group, as-indacenyl group, acenaphthylenyl group, acenaphthenyl group, acenaphthoquinonyl group , Phenalenyl group, naphthacenyl group, chrycenyl Group, pyrenyl group, triphenylenyl group, benzo [a] anthracenyl group, benzo [a] anthraquinonyl group, aceanthrenyl group, aceanthrenyl group, aceanthrenequinolyl group, acephenanthrenylenyl group, fluoranthenyl group, Examples include a preadenyl group, a pentacenyl group, a perylenyl group, a picenyl group, and a benzo [a] pyrenyl group. Among these, a condensed polycyclic hydrocarbon group having 2 or 3 rings is preferable because of easy availability and a decrease in difficulty of synthesis, but is not limited thereto. In addition, the substituted or unsubstituted condensed polycyclic hydrocarbon group may be bonded to the carbon atom of the general formula (1) at any substitution position, and at a substitution position capable of forming a covalent bond with the carbon atom. If there is, there is no particular limitation.

Examples of the substituent that the heterocyclic group and the condensed polycyclic hydrocarbon group may have include a hydroxyl group, a mercapto group, a cyano group, a nitro group, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, and an acyl group. , Alkoxyl group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylthio group, arylthio group, heterocyclic thio group, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, alkylarylamino group , Benzylamino group, dibenzylamino group and the like.
Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkyl group include linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 18 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, and pentyl. Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group Group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like.

Examples of the aryl group include monocyclic or condensed polycyclic aryl groups having 6 to 18 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, and a 9-phenanthryl group. 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 9-fluorenyl group and the like.
Examples of the heterocyclic group include a monocyclic or condensed polycyclic heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a 2-furanyl group, a 2-thienyl group, 2- Indolyl group, 3-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-acridinyl group and the like can be mentioned.

  The acyl group includes a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic or condensed polyvalent group having 6 to 18 carbon atoms. Examples include a carbonyl group to which a cyclic aryl group is bonded, a carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. It may have an unsaturated bond, and specific examples thereof include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group , Stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoy Group, isocrotonoyl group, oleoyl group, benzoyl group, 2-methylbenzoyl group, 4-methoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, An isonicotinoyl group, a 9-anthroyl group, a 5-naphthacenoyl group, etc. are mentioned.

  Examples of the alkoxyl group include linear, branched, monocyclic or condensed polycyclic alkoxyl groups having 1 to 18 carbon atoms. Specific examples include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy. Group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, t-butoxy group, sec-pentyloxy group, t-pentyloxy group, t-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group , Boronyloxy group, 4-decyl Cyclohexyloxy group, 2-tetrahydrofuranyl group, 2-tetrahydrofuranyl group, and the like.

Examples of the aryloxy group include monocyclic or condensed polycyclic aryloxy groups having 6 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and 9-anthryloxy. Group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, etc. Is mentioned.
Examples of the heterocyclic oxy group include a monocyclic or condensed polycyclic heterocyclic oxy group containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a 2-furanyloxy group and a 2-thienyloxy group. 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group, 3-carbazolyloxy group, 4-carbazolyl group An oxy group, 9-acridinyloxy group, etc. are mentioned.

  The acyloxy group includes a carbonyloxy group to which a hydrogen atom or a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic or condensed group having 6 to 18 carbon atoms. A carbonyloxy group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, including a carbonyloxy group to which a polycyclic aryl group is bonded, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom; Specific examples include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentyl Carbonyloxy group, cyclohexylcarbonyloxy group, acrylo Ruoxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anthroyloxy group, 5-naphthathenoyloxy group and the like.

Examples of the alkylthio group include linear, branched, monocyclic or condensed polycyclic alkylthio groups having 1 to 18 carbon atoms, and specific examples include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and a pentylthio group. Hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like.
Examples of the arylthio group include monocyclic or condensed polycyclic arylthio groups having 6 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and a 9-phenanthri group. And a ruthio group.
Examples of the heterocyclic thio group include a monocyclic or condensed polycyclic heterocyclic thio group containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a 2-furylthio group, a 2-thienylthio group, Examples include 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, 3-carbazolylthio group, 4-carbazolylthio group and the like.

  Examples of the alkylamino group include methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group, octadecylamino group Group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentylamino group, Cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantamino group, etc. It is below.

  Dialkylamino group includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, And piperazino group.

Examples of the arylamino group include an N-arylamino group, anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3- Biphenylamino group, 4-biphenylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group and the like can be mentioned.
Examples of the diarylamino group include a diarylamino group, a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.
Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like.

  Furthermore, the hydrogen atom of the substituent that the above-described heterocyclic group and condensed polycyclic hydrocarbon group may have may be further substituted with another substituent. Examples of such a substituent include Halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryloxy groups such as phenoxy group and p-tolyloxy group, methoxycarbonyl group and butoxycarbonyl Group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acyl group such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methoxalyl group, methylsulfanyl Group, tert-butylsulfanyl group and the like Arylsulfanyl groups such as sulfanyl group, phenylsulfanyl group, p-tolylsulfanyl group, alkylamino groups such as methylamino group, cyclohexylamino group, dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group, piperidino group, phenyl Aryl group such as amino group, p-tolylamino group, alkyl group such as methyl group, ethyl group, tert-butyl group, dodecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group In addition to aryl groups such as phenanthryl group, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloro Methyl group, trimethylsilyl , Phosphinico group, a phosphono group, trimethyl ammonium Niu mill group, dimethylsulfoxide Niu mill group, triphenyl phenacyl phosphonium Niu mill group, and the like.

Furthermore, the substituents in A and B may be combined with other substituents or hydrogen atoms on the ring to form a cyclic structure.
A and B may be integrated to form an annular structure.

  Next, X in the general formula (1) will be described. X represents a monovalent organic residue. The monovalent organic residue may have an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. An alkynyl group, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, a heterocyclic oxy group that may have a substituent, an acyloxy group that may have a substituent, 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, substituent An alkylsulfonyl group that may have a substituent, an arylsulfonyl group that may have a substituent, an acyl group that may have a substituent, an alkoxycarbonyl group that may have a substituent, and a substituent May be carbamoyl , An optionally substituted sulfamoyl group, an optionally substituted amino group, an optionally substituted phosphinoyl group, and heterocyclic group which may have a substituent.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl 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-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-nitrophenacyl group Etc. The.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable, and a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , M-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, Phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthra Nyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.
The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.
The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, for example, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, or a sec-butoxy group. T-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-octylaminocarbonyl Yloxy group, N- methyl -N- benzylaminocarbonyl methyloxy group, a benzyloxy group, and a cyanomethyloxy group.

  The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group, Examples include 4-fluorophenyloxy group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, 4-phenylsulfanylphenyloxy group, and the like.

Examples of the heterocyclic oxy group that may have a substituent include a monocyclic or condensed polycyclic heterocyclic oxy group containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-carbazolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 3-carbazolyl An oxy group, 4-carbazolyloxy group, 9-acridinyloxy group, etc. are mentioned.
The acyloxy group which may have a substituent is preferably an acyloxy group having 2 to 20 carbon atoms, such as an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, or trifluoromethylcarbonyloxy. Group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

  The alkylsulfanyl group which may have a substituent is preferably an alkylsulfanyl group having 1 to 20 carbon atoms. For example, a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, a butylsulfanyl group, or a hexylsulfanyl group. Group, cyclohexylsulfanyl group, octylsulfanyl group, 2-ethylhexylsulfanyl group, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, methoxymethylsulfanyl group and the like.

  The arylsulfanyl group which may have a substituent is preferably an arylsulfanyl group having 6 to 30 carbon atoms, such as a 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-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfuric group Aniru group, 4-dimethylamino-phenylsulfanyl group and the like.

  The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. For example, a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, and a hexylsulfinyl group. Group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methoxymethylsulfinyl group and the like.

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, such as a 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-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfuric group Iniru group, 4-dimethylaminophenyl sulfinyl group and the like.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. For example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group. Group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group and the like.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 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-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminopheny Sulfonyl group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl 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-methoxybenzoyl Groups and the like.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyl. Oxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4- Phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group 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 and the like.

  The carbamoyl group which may have a substituent is preferably a carbamoyl group having 1 to 30 carbon atoms, for example, an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, or an N-butylcarbamoyl group. N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2- Chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenyl A carbamoyl group, -4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N -Dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like.

  The sulfamoyl group which may have a substituent is preferably a sulfamoyl group having 0 to 30 carbon atoms, for example, a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, N, N- Examples thereof include a dialkylsulfamoyl group, an N, N-diarylsulfamoyl group, and an N-alkyl-N-arylsulfamoyl group. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like.

The amino group which may have a substituent is preferably an amino group having 0 to 50 carbon atoms in total, for example, —NH ₂ , N-alkylamino group, N-arylamino group, N-acylamino group, N— Examples include sulfonylamino group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group and the like. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, Nt-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-cyanophenylamino group, N-3-trifluoromethylphenylamino group, -4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino group, N- 4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino 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 and the like.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group. Group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Furthermore, the alkyl group which may have a substituent mentioned above, the aryl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, a substituent An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an acyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, and a substituent An arylsulfanyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent. An arylsulfonyl group, an optionally substituted acyl group, an optionally substituted alkoxycarbonyl group, an optionally substituted carbamoyl group, an optionally substituted sulfamoyl group, Amino group which may have a group, hydrogen atom of the heterocyclic group which may have a substituent may be further substituted with other substituents.

  Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryl groups such as phenoxy group and p-tolyloxy group. Oxy group, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, Acyl group such as methoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, cyclohexyla Alkyl groups such as alkyl groups, dimethylamino groups, diethylamino groups, morpholino groups, piperidino groups and other dialkylamino groups, phenylamino groups, p-tolylamino groups and other arylamino groups, methyl groups, ethyl groups, tert-butyl groups In addition to alkyl groups such as dodecyl group, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, etc., hydroxy groups, carboxy groups, formyl groups, mercapto groups, Sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfonyl group, Triphenylphenacylphosphoniumyl group, etc. And the like.

  X is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, a phosphinyl group which may have a substituent, a substituted group It is a heterocyclic group which may have a group. X is more preferably an alkyl group which may have a substituent, or an aryl group which may have a substituent. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, A t-butyl group, a trifluoromethyl group, a phenyl group, a benzyl group and the like can be mentioned, but the examples are not limited to these examples.

In the photopolymerization initiator represented by the general formula (1) of the present invention, it is preferable that A and B in the general formula (1) are not the same from the viewpoint of solubility or sensitivity.
Further, among the photopolymerization initiators represented by the general formula (1), it is more preferable that A in the general formula (1) is a substituted or unsubstituted carbazolyl group, or a substituted or unsubstituted naphthyl group. It is a polymerization initiator. In this case, the carbazolyl group and the naphthyl group may be bonded at any substitution position as long as they can form a covalent bond with the adjacent carbon atom of the general formula (1). Examples of the substituent that the carbazolyl group or naphthyl group may have include the same substituents as those exemplified for the substituent that A and B may have. Further, a part of substituents on the carbazolyl group and naphthyl group may be bonded to a carbon atom of the carbazolyl group or naphthyl group or a part of another substituent to form a ring structure.

  Of the photopolymerization initiators represented by the general formula (1), it is more preferable that A in the general formula (1) is a group represented by the substituted or unsubstituted general formula (2) or a substituted or unsubstituted group. The photopolymerization initiator of the group represented by the general formula (3). The groups represented by the general formula (2) and the general formula (3) are bonded at any substitution position as long as they can form a covalent bond with the adjacent carbon atom of the general formula (1). May be.

一般式（３）

General formula (2)

General formula (3)

In the general formula (2), Y represents a monovalent organic residue, and examples thereof include the same monovalent organic residue as X in the general formula (1). From the standpoint of ease, a substituted or unsubstituted alkyl group is preferred.
Of the photopolymerization initiators represented by the general formula (1), particularly preferred is A in the general formula (1) is a group represented by the substituted or unsubstituted general formula (2), and B is It is a photopolymerization initiator of a group represented by the general formula (3) which is substituted or unsubstituted.

The hydrogen atom of the group represented by the general formula (2) and the group represented by the general formula (3) may be substituted with a substituent, and as such a substituent, A and B have And the same substituents as those mentioned above for the good substituent. The substituent in the general formula (2) is preferably an acyl group, more preferably a substituted or unsubstituted benzoyl group or a substituted or unsubstituted alkylcarbonyl group.
Although the specific structure of the photoinitiator represented by General formula (1) in this invention is shown in Table 1, the structure of a photoinitiator is not limited to them.

The starting material for synthesizing the photopolymerization initiator represented by the general formula (1) is an oxime represented by the following general formula (4).
General formula (4)

(In the formula, A and B have the same meanings as A and B in the general formula (1).)
The oxime represented by the general formula (4) is described in, for example, Org. React., 7, <1953>, 327, edited by The Chemical Society of Japan, 4th edition, Experimental Chemistry Course, Vol. 14, page 1316 (Maruzen). It can be obtained by various methods. Furthermore, it can also be obtained from a method for synthesizing oximes described in commercially available chemistry texts (for example, J. March, Advanced Organic Organic Chemistry, 4th Edition, Wiley Interscience, 1992).

One of the most convenient methods of synthesizing oximes is nitrosation of active methylene groups with nitrous acid or alkyl nitrites. The reaction conditions are, for example, Organic Syntheses Coll.
VI, pp 840, Organic Syntheses Coll. Vol. III, pp 191 and 513, Organic Syntheses
Vol. II, pp 202, 204 and 363, J. Am. Chem. Soc., 47, <1925>, 2033, J. Chem. Soc., 117, <1920>, 590, J. Am. Chem Soc., 51, <1929>, 2264, which is suitable for the production of oximes. Nitrous acid is usually produced from sodium nitrite. The nitrite alkyl ester is, for example, methyl nitrite, isopropyl nitrite, butyl nitrite, isoamyl nitrite.

The photopolymerization initiator represented by the general formula (1) is a method described in the literature, for example, an oxime and an acyl chloride or an acid obtained by the above-described method using the oxime represented by the general formula (4) as a starting material. Prepared by reacting with an anhydride in an inert solvent such as tetrahydrofuran, benzene or dimethylformamide, in the presence of a base, for example a tertiary amine such as triethylamine, or in a basic solvent such as pyridine. Is done.
Such reactions are known to those skilled in the art and are generally carried out at -15 ° C to + 50 ° C, preferably 0-30 ° C.

All oxime ester groups exist in two configurations, (Z) or (E). Although this isomer can be separated by a conventional method, a mixture of isomers can also be used as a photopolymerization initiator. Therefore, in the present invention, the compound of the general formula (1) may be a mixture of configurational isomers.
The photopolymerization initiator represented by the general formula (1) of the present invention can be identified by elemental analysis values and ¹ H-NMR.

The photopolymerization initiator represented by the general formula (1) can be used in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight, with respect to 100 parts by weight of the dye in the photosensitive coloring composition. .
In the photosensitive coloring composition of this invention, another photoinitiator can be used together with the photoinitiator represented by the said General formula (1).

  Other photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, Acetophenone compounds such as 1-hydroxycyclohexyl phenyl ketone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Benzoin compounds such as benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, Thioxanthone compounds such as 4-diisopropylthioxanthone and 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- ( p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6- Bis (trichloromethyl) -s-triazine, 2,4-bis ( Lichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl- (4′-methoxystyryl) -6-triazine Compound, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4 Oxime ester compounds such as' -methoxy-naphthyl) ethylidene) hydroxylamine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2 Phosphine compounds such as 1,4,6-trimethylbenzoyldiphenylphosphine oxide, quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds A compound or the like is used. These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. The other photopolymerization initiator can be used in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight, with respect to 100 parts by weight of the dye in the photosensitive coloring composition.

Furthermore, the photosensitive coloring composition of the present invention can contain a sensitizer. The sensitizer can be used in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator in the colored composition.
Sensitizers include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler's ketone derivatives and the like.

Furthermore, Okawara Nobu et al. “Dye Handbook” (1986, Kodansha), Okawara Nobu et al. “Functional Dye Chemistry” (1981, CMC), Ikemori Tadasaburo et al. “Special Functional Materials” (1986, Examples of the sensitizer described in CMC) are not limited thereto. In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.
Two or more kinds of sensitizers may be used in combination at any ratio as required.

  Among the sensitizers, examples of the sensitizer capable of particularly suitably sensitizing the photopolymerization initiator represented by the general formula (1) include thioxanthone derivatives and Michler ketone derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is preferably used.

Moreover, the photosensitive coloring composition of the present invention can contain an amine compound having a function of reducing dissolved oxygen.
Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine and the like.

As described above, the dye carrier contained in the photosensitive coloring composition of the present invention is composed of a transparent resin and a precursor thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and its precursor includes a monomer or an oligomer that is cured by irradiation with radiation to form a transparent resin. Or a mixture of two or more.
The transparent resin can be used in an amount of 20 to 400 parts by weight, preferably 50 to 250 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition. The precursor of the transparent resin can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, with respect to 100 parts by weight of the pigment in the colored composition.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Photosensitive resins include (meth) acrylic compounds and cinnamic acid having reactive substituents such as isocyanate groups, aldehyde groups, and epoxy groups on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups. And a resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  Monomers and oligomers that are precursors of transparent resins include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β -Carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (me Acrylate), neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy ( Various acrylic and methacrylic esters such as (meth) acrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxy Examples include methyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. These can be used alone or in admixture of two or more.

In the photosensitive coloring composition, the ratio M / P of the weight (P) of the transparent resin and the weight (M) of the precursor is preferably 0.10 to 1.20, and 0.20 to 1. 00 is more preferable, and 0.25 to 0.60 is particularly preferable. When M / P is less than 0.10, the sensitivity is low, and when M / P exceeds 1.20, pattern shape linearity failure, tackiness, or the like occurs.
The ratio I _a / M of the weight (I _a ) of the photopolymerization initiator and the weight (M) of the precursor of the transparent resin is preferably 0.20 to 1.50, preferably 0.25 to 1 .40 is more preferable, and 0.30 to 1.30 is particularly preferable.

Further, when the photosensitive coloring composition contains a sensitizer, the ratio of the total weight (I _b ) of the photopolymerization initiator and the sensitizer to the weight (M) of the precursor of the transparent resin I _b / M is preferably 0.20 to 1.50, more preferably 0.23 to 1.00, and particularly preferably 0.25 to 0.60.
When I _a / M and I _b / M are less than 0.20, the sensitivity is low, and when I _a / M and I _b / M exceeds 1.50, a pattern-shaped linearity defect occurs.

As a pigment | dye contained in the photosensitive coloring composition of this invention, an organic or inorganic pigment can be used individually or in mixture of 2 or more types. Among the pigments, pigments having high color developability and high heat resistance, particularly pigments having high heat decomposition resistance are preferred, and organic pigments are usually used.
Below, the specific example of the organic pigment which can be used for the photosensitive coloring composition of this invention is shown with a color index number.

  Examples of the red photosensitive coloring composition for forming the red filter segment include CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81. : 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220 Red pigments such as 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, 272, and 279 can be used. A yellow pigment and an orange pigment can be used in combination with the red photosensitive coloring composition.

  For example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18 may be used as the yellow photosensitive coloring composition for forming the yellow filter segment. 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166 167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc. Can be used.

Orange pigments such as CI Pigment orange 36, 43, 51, 55, 59, 61, 71, 73 can be used for the orange photosensitive coloring composition for forming the orange filter segment.
As the green photosensitive coloring composition for forming the green filter segment, for example, a green pigment such as CI Pigment Green 7, 10, 36, 37 can be used. A yellow pigment can be used in combination with the green photosensitive coloring composition.

  Blue photosensitive coloring compositions for forming blue filter segments include, for example, CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64. , 80 and the like can be used. Purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination with the blue photosensitive coloring composition.

For example, CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 or the like is used as a cyan photosensitive coloring composition for forming a cyan filter segment. Can be used.
As the magenta color photosensitive coloring composition for forming the magenta color filter segment, purple pigments and red pigments such as CI Pigment Violet 1, 19, CI Pigment Red 81, 144, 146, 177, 169 can be used. . A yellow pigment can be used in combination with the magenta photosensitive coloring composition.

  Examples of the black photosensitive coloring composition for forming the black matrix include carbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically CI pigment black 1, 6, 7, 12, 20, 31 or the like can be used. For the black photosensitive coloring composition, a mixture of a red pigment, a blue pigment, and a green pigment can also be used. As the black pigment, carbon black is preferable from the viewpoint of price and light shielding properties, and the carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust a color tone, a blue pigment and a purple pigment can be used together in a black photosensitive coloring composition.

Carbon black having a specific surface area of 50 to 200 m ² / g by the BET method is preferable from the viewpoint of the shape of the black matrix. When carbon black having a specific surface area of less than 50 m ² / g is used, the black matrix shape is deteriorated. When carbon black of more than 200 m ² / g is used, the dispersion aid is excessively adsorbed on the carbon black. This is because it is necessary to add a large amount of a dispersion aid in order to express various physical properties.
Carbon black preferably has an oil absorption of dibutyl phthalate (hereinafter referred to as “DBP”) of 120 ml / 100 g or less from the viewpoint of sensitivity.
Furthermore, it is preferable that the average primary particle diameter of carbon black is 20-50 nm. Carbon black having an average primary particle diameter of less than 20 nm is difficult to disperse at a high concentration, and it is difficult to obtain a photosensitive black composition having good stability over time. This is because the matrix shape may be deteriorated.

Also, inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black. Examples thereof include metal oxide powders such as synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.
The photosensitive coloring composition of the present invention may contain a dye within a range that does not reduce heat resistance for color matching.

  In the photosensitive coloring composition of the present invention, the dye is sufficiently dispersed in the dye carrier, and applied to a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 10 μm. A solvent can be included to facilitate the formation of the matrix. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone. , Ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent and the like, and these are used alone or in combination.

The photosensitive coloring composition of the present invention includes one or more dyes, together with the photopolymerization initiator, in a dye carrier and a solvent such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor. It can be produced by finely dispersing using a dispersing means. Moreover, the photosensitive coloring composition containing 2 or more types of pigment | dyes can also mix and manufacture what each disperse | distributed finely in the pigment | dye carrier and a solvent separately. When the dye is dispersed in the dye carrier and the solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, and a dye derivative can be appropriately contained. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, a photosensitive coloring composition obtained by dispersing the pigment in a dye carrier and a solvent using the dispersion aid is used. When used, a color filter excellent in transparency can be obtained.
The dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

  The resin-type pigment dispersant has a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the dye carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the dye carrier. It works. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more.

  The dye derivative is a compound in which a substituent is introduced into an organic dye, and the organic dye includes light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.

  The photosensitive coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time, and in order to improve the adhesion to the transparent substrate, such as a silane coupling agent. An adhesion improver can also be included. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite.

Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane.
The silane coupling agent can be used in an amount of 0.1 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the dye in the photosensitive coloring composition.

The photosensitive coloring composition of the present invention can be prepared in the form of a solvent developing type or alkali developing type colored resist material. The colored resist material is obtained by dispersing a pigment in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, a monomer, a photopolymerization initiator, and a solvent.
The pigment is preferably contained in a proportion of 5 to 70% by weight based on the total solid content of the photosensitive coloring composition. More preferably, it is contained in a proportion of 20 to 50% by weight, and the remainder consists essentially of a resinous binder provided by a dye carrier.
The photosensitive coloring composition is obtained by means of centrifugal separation, sintering filter, membrane filter or the like, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more and mixed dust. Is preferably removed.

Next, the color filter of the present invention will be described.
The color filter of the present invention comprises a filter segment or a black matrix formed from the photosensitive coloring composition of the present invention on a transparent substrate, and a general color filter has at least one red filter segment, at least It comprises one green filter segment and at least one blue filter segment, or comprises at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.

As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.
The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

  Formation of each color filter segment and black matrix by photolithography is performed by the following method. That is, the photosensitive coloring composition prepared as a solvent developing type or alkali developing type colored resist material has a dry film thickness of 0. 0 on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It apply | coats so that it may become 2-10 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Thereafter, the filter segment and the black matrix can be formed by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove uncured portions and forming a desired pattern. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, it is possible to form a filter segment and a black matrix with higher accuracy than the printing method.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase the UV exposure sensitivity, the colored resist material is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples and comparative examples, “parts” means “parts by weight”.
First, the preparation of the acrylic resin solution used in Examples and Comparative Examples and the synthesis of a photopolymerization initiator will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

[Preparation of acrylic resin solution]
370 parts of cyclohexanone was put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate at the same temperature, A mixture of 15.0 parts of 2-hydroxyethyl methacrylate and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained.
After cooling to room temperature, about 2 g of acrylic resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized acrylic resin solution so that the nonvolatile content was 20% by weight. Added. The weight average molecular weight of the obtained acrylic resin was 40000.

[Synthesis of Photopolymerization Initiator A-1]
When 25.0 parts of 1,3-bis- (4-methoxy-naphthalen-1-yl) -propane-1,3-dione was dissolved in a mixed solution of 250 parts of tetrahydrofuran and 125 parts of concentrated hydrochloric acid, the mixture was stirred at room temperature. Below, 7.50 parts of tert-butyl nitrite was added dropwise over 45 minutes. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 800 parts of ice water and extracted with 750 parts of chloroform. The organic layer was washed with water (500 parts × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to give 1,3-bis- (4-Methoxy-naphthalen-1-yl) -propane-1,2,3-trione 2-oxime was obtained. Next, 18.0 parts of 1,3-bis- (4-methoxy-naphthalen-1-yl) -propane-1,2,3-trione 2-oxime and 3.34 parts of sodium acetate are added in 300 parts of benzene. Was added to 5.0 parts of acetic anhydride, and the mixture was heated to reflux for 4 hours. Thereafter, the reaction solution is poured into 500 parts of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (300 parts × 3 times), dried over magnesium sulfate, the desiccant is filtered and the solvent is distilled off. The residue was recrystallized with ethyl acetate-hexane to obtain a photopolymerization initiator A-1.

[Synthesis of Photopolymerization Initiator A-2]
1,3-bis- (4-methoxy-naphthalen-1-yl) -propane-1,3-dione is converted to 1,3-bis- (4-ethoxy-naphthalen-1-yl) -propane-1,3- Photopolymerization initiator A-2 was obtained in the same manner as photopolymerization initiator A-1, except that it was changed to dione.
[Synthesis of Photopolymerization Initiator A-3]
Except for changing 1,3-bis- (4-methoxy-naphthalen-1-yl) -propane-1,3-dione to 1,3-dithiophen-2-yl-propane-1,3-dione, light Photopolymerization initiator A-3 was obtained in the same manner as polymerization initiator A-1.

[Synthesis of Photopolymerization Initiator A-4]
1,3-bis- (4-methoxy-naphthalen-1-yl) -propane-1,3-dione to 1-furan-2-yl-3-thiophen-2-yl-propane-1,3-dione Photopolymerization initiator A-4 was obtained in the same manner as photopolymerization initiator A-1, except that the change was made.
[Synthesis of Photopolymerization Initiator A-5]
1,3-bis- (4-methoxy-naphthalen-1-yl) -propane-1,3-dione is converted to 1- (4-methoxy-naphthalen-1-yl) -3-thiophen-2-yl-propane- Photopolymerization initiator A-5 was obtained in the same manner as photopolymerization initiator A-1, except that it was changed to 1,3-dione.

[Synthesis of Photopolymerization Initiator A-6]
1,3-bis- (4-methoxy-naphthalen-1-yl) -propane-1,3-dione is converted to 1- (4-methoxy-naphthalen-1-yl) -3-naphthalen-1-yl-propane- Photopolymerization initiator A-6 was obtained in the same manner as photopolymerization initiator A-1, except that it was changed to 1,3-dione.
[Synthesis of Photopolymerization Initiator A-7]
1,3-bis- (4-methoxy-naphthalen-1-yl) -propane-1,3-dione is converted to 1- (9-ethyl-9H-carbazol-3-yl) -3-naphthalen-1-yl- Photopolymerization initiator A-7 was obtained in the same manner as photopolymerization initiator A-1, except that it was changed to propane-1,3-dione.

[Synthesis of Photopolymerization Initiator A-8]
1,3-bis- (4-methoxy-naphthalen-1-yl) -propane-1,3-dione is converted to 1- [9- (2-ethoxyethyl) -6- (2-methyl-benzoyl) -9H- Photopolymerization initiator A-8 was obtained in the same manner as photopolymerization initiator A-1, except that it was changed to carbazol-3-yl] -3-naphthalen-1-yl-propane-1,3-dione.

The structural formula of the obtained photopolymerization initiator is shown in Table 2.

先に調製したアクリル樹脂溶液 ４０．０部
シクロヘキサノン ４８．０部 [Adjustment of red pigment dispersion]
A mixture having the following composition was stirred and mixed uniformly, then dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), and then filtered with a 5 μm filter to prepare a red pigment dispersion.
11.0 parts of diketopyrrolopyrrole pigment (CI Pigment Red 254) ("Irga Four Red B-CF" manufactured by Ciba Specialty Chemicals)
1.0 part of the following diketopyrrolopyrrole pigment derivative

Acrylic resin solution prepared earlier 40.0 parts Cyclohexanone 48.0 parts

[Adjustment of green pigment dispersion]
A green pigment dispersion was prepared in the same manner as the red pigment dispersion except that the pigment was changed to the following pigment and the pigment derivative was changed to the following pigment derivative.
7.1 parts of halogenated copper phthalocyanine pigment (CI Pigment Green 36) (“Rionol Green 6YK” manufactured by Toyo Ink Co., Ltd.)
Monoazo pigment (CI Pigment Yellow 150) 3.9 parts ("E4GN-GT" manufactured by LANXESS)
1.0 part of the following triazine pigment derivative

[Adjustment of blue pigment dispersion]
A blue pigment dispersion was prepared in the same manner as the red pigment dispersion except that the pigment was changed to the following pigment and the pigment derivative was changed to the following pigment derivative.
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) 11.0 parts (“Heliogen Blue L-6700F” manufactured by BASF)
1.0 part of the following phthalocyanine pigment derivative

[Adjustment of black pigment dispersion]
A black pigment dispersion was prepared in the same manner as the red pigment dispersion except that the pigment was changed to the following pigment.
Carbon black ("MA77" manufactured by Mitsubishi Chemical Corporation) 12.0 parts

[Examples 1 to 22 and Comparative Examples 1 to 4] (Adjustment of photosensitive coloring composition)
With the blending composition shown in Table 3, the mixture was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain each color resist material.

Monomer: Trimethylolpropane triacrylate
(Shin Nakamura Chemical "NK Ester ATMPT")
Photoinitiator A: Compound in Table 2 A-1
Photopolymerization initiator B: Compound A-2 in Table 2
Photopolymerization initiator C: Compound A-3 in Table 2
Photopolymerization initiator D: Compound A-4 in Table 2
Photopolymerization initiator E: Compound A-5 in Table 2
Photopolymerization initiator F: Compound A-6 in Table 2
Photoinitiator G: Compound A-7 in Table 2
Photopolymerization initiator H: Compound A-8 in Table 2
Photoinitiator I: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (“Irgacure 369” manufactured by Ciba Specialty Chemicals) Sensitizer J: 2,4- Diethylthioxanthone

[Filter segment and black matrix pattern formation]
The obtained resist material was applied to a 10 cm × 10 cm glass substrate by spin coating so that the film thickness after post-baking was as shown in Table 4, and then pre-baked at 70 ° C. for 15 minutes in a clean oven. did. Next, after cooling the substrate to room temperature, ultraviolet rays were exposed through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, and air-dried. Thereafter, post-baking was performed at 230 ° C. for 30 minutes in a clean oven to form a stripe-shaped filter segment or black matrix on the substrate.

[Evaluation]
The sensitivity of the obtained resist material and the pattern shape of the filter segment or black matrix formed by the above method were evaluated by the following methods. The results are shown in Table 4.
(sensitivity)
The sensitivity of the resist was determined by the irradiation exposure amount at which the formed filter segment or black matrix pattern was finished according to the image size of the photomask. The rank of evaluation is as follows.
○: Less than 100 mJ / cm ² Δ: 100 mJ / cm ² or more and less than 300 mJ / cm ² ×: 300 mJ / cm ² or more

(Pattern shape)
The shape of the formed filter segment or black matrix pattern was evaluated by (1) the linearity of the pattern and (2) the cross-sectional shape of the pattern.
(1) was evaluated by observing with an optical microscope. The rank of evaluation is as follows.
◯: Good linearity Δ: Partially good linearity ×: Poor linearity (2) was evaluated by observing with a scanning electron microscope (SEM). The rank of evaluation is as follows.
○: Forward tapered shape.
Δ: Non-tapered shape.
X: Reverse taper shape.

(Solubility evaluation)
Five parts of an initiator were added to 100 parts of cyclohexanone, stirred with a disper and evaluated in three stages.
○: Dissolved within 5 minutes after stirring Δ: Dissolved between 5 minutes and 10 minutes after stirring ×: Not dissolved even after 10 minutes after stirring

Film thickness: film thickness of each color filter segment and black matrix.
Dye content: Ratio of dye based on the total solid content of the photosensitive coloring composition.
M / P = (Weight of transparent resin precursor) / (Weight of acrylic resin)
I _a / M = (weight of photopolymerization initiator) / (weight of transparent resin precursor)
I _b / M = (total weight of photopolymerization initiator and sensitizer) / (weight of transparent resin precursor)

As shown in Table 4, the photosensitive coloring compositions of Examples 1 to 22 using the photopolymerization initiator represented by the general formula (1) have high sensitivity, and the linearity of the obtained pattern. The cross-sectional shape was also good. Among them, A in the general formula (1) is a group represented by a substituted or unsubstituted general formula (2), and B is a group represented by a substituted or unsubstituted general formula (3). The photosensitive coloring compositions of Examples 8 to 22 using the compound had higher sensitivity and good solubility in the solvent.
On the other hand, the photosensitive coloring compositions of Comparative Examples 1 to 4 using other photopolymerization initiators are poor in sensitivity, pattern linearity, or cross-sectional shape, and all are good. Nothing was obtained.

Claims (6)

A photosensitive coloring composition comprising a dye carrier comprising a transparent resin and a precursor thereof, a dye, and a photopolymerization initiator represented by the following general formula (1).
General formula (1)

(In the formula, A and B each independently represent a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed polycyclic hydrocarbon group, and X represents a monovalent organic residue.)   2. The photosensitive property according to claim 1, wherein the ratio (M / P) of the weight (P) of the transparent resin and the weight (M) of the precursor of the transparent resin is 0.10 to 1.20. Coloring composition. The ratio (I _a / M) between the weight (I _a ) of the photopolymerization initiator and the weight (M) of the precursor of the transparent resin is 0.20 to 1.50, or 2. The photosensitive coloring composition according to 2. Further, a sensitizer is included, and the ratio (I _b / M) of the total weight (I _b ) of the photopolymerization initiator and the sensitizer to the weight (M) of the precursor of the transparent resin is 0.20 to 1. It is 50, The photosensitive coloring composition of any one of Claims 1-3 characterized by the above-mentioned.   A color filter comprising a filter segment formed from the photosensitive coloring composition according to claim 1 on a transparent substrate. A color filter comprising a black matrix formed from the photosensitive coloring composition according to any one of claims 1 to 4 on a transparent substrate.