WO2008035671A1 - Photosensitive coloring composition and color filter - Google Patents

Abstract

A photosensitive coloring composition comprises: a carrier for a coloring agent, which comprises a transparent resin and a precursor thereof; the coloring agent; and a photopolymerization initiator represented by the general formula (1). A color filter comprises a transparent substrate and a filter segment or black matrix made of the photosensitive coloring composition. [General formula (1)] wherein A and B independently represent a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted fused polycyclic hydrocarbon group; and X represents a univalent organic residue.

Description

 Specification

 Photosensitive coloring composition and color filter

 Technical field

 TECHNICAL FIELD [0001] The present invention relates to a photosensitive coloring composition, and in particular for color filters used in liquid crystal display devices and solid-state imaging devices, each color filter segment such as red, green, blue, yellow, orange, cyan, magenta, and black matrix. It is related with the highly sensitive photosensitive coloring composition useful for formation of the above. The present invention also relates to a color filter formed using the photosensitive coloring composition.

 Background art

 [0002] A color filter includes two or more kinds of fine stripe-shaped filter segments of different colors formed on the surface of a transparent substrate such as glass. These filter segments are arranged parallel to or crossing each other, or arranged in a constant vertical and horizontal arrangement. The filter segments have a fine width of several microns to several hundred microns, and are arranged in a predetermined arrangement for each hue.

 In general, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on the color filter by vapor deposition or sputtering, and the liquid crystal is aligned in a certain direction on the transparent electrode. An alignment film is formed. In order to obtain sufficient performance of these transparent electrodes and alignment films, their formation must generally be performed at a high temperature of 200 ° C or higher, preferably 230 ° C or higher.

 [0004] For this reason, 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 currently the mainstream.

 [0005] In 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. Next, remove the unexposed areas in the development process to form the first color pattern, apply heat treatment if necessary, and then repeat the same operation for the remaining filter colors. Thus, a color filter can be manufactured.

In recent years, color liquid crystal display devices have been used for liquid crystal color televisions, car navigation systems, and A large market has been formed for notebook personal computers with integrated liquid crystal display devices, and it has begun to spread as monitors and televisions for desktop computers that take advantage of energy and space saving features. Color liquid crystal display devices are attracting attention as an alternative to conventional CRTs, but at present, the color reproduction characteristics of liquid crystal display devices are inferior to those of CRTs!

 [0007] Therefore, there is an increasing demand for high color reproducibility in a color filter in which filter segments for each color are arranged.

 [0008] In order to improve contrast, a black matrix is generally arranged between filter segments of each color of the color filter. As a material for forming this black matrix, in recent years, from the viewpoint of environmental problems, low reflection, and low cost, a resin black matrix in which a light-shielding colorant is dispersed in a resin has attracted attention instead of a metal chromium black matrix. ing. However, the resin black matrix has a problem of low light shielding (optical density) compared to black matrix made of chromium metal.

 [0009] In order to improve the color reproduction characteristics of the color filter and the light-shielding property of the black matrix, the content of the colorant in the photosensitive coloring composition is increased, or the photosensitive coloring composition It is necessary to increase the coating film thickness. However, when the content of the colorant is increased, the sensitivity is lowered, and problems such as deterioration in developability and resolution occur. If the film thickness is increased, the exposure light does not reach the bottom of the film, causing problems such as poor pattern shape.

In order to solve such problems, 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 and a sensitizer are selected or increased, and (3) a monomer is selected or increased. For example, JP 2001-233842 A discloses a photoinitiator made of a specific oxime ester compound, and JP 2001-264530 A discloses a photo radical generator made of a specific oxime ester compound. JP-A 2003-156842 discloses the use of a photopolymerization initiator composed of aacetophenone compound and a triazine compound and a photopolymerization initiation assistant composed of an amine.

[0011] However, addition of a double bond to the resin, photopolymerization initiator, sensitizer, and monomer There is a limit to the improvement of sensitivity only by selecting this. In particular, when the amount of the photopolymerization initiator is increased, coloring due to the unique color of 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.

 Disclosure of the invention

 [0012] The present invention provides a photosensitive coloring composition that gives an excellent pattern shape with high sensitivity even when the colorant content is high or when it is applied with a thick film, and a color filter using the same. The purpose is to provide.

[0013] According to the present invention, the photosensitive coloring composition is highly sensitive and uses a photopolymerization initiator represented by the following general formula (1) in order to obtain an excellent pattern shape. Features.

 That is, according to the first aspect of the present invention, a photosensitive coloring containing a colorant carrier comprising a transparent resin and its precursor, a colorant and a photopolymerization initiator represented by the following general formula (1) A composition is provided.

[0015] In addition, according to the second aspect of the present invention, there is provided a color filter comprising a filter segment formed from the photosensitive coloring composition of the present invention.

Furthermore, according to the third aspect of the present invention, there is provided a color filter comprising a black matrix formed from the photosensitive coloring composition of the present invention.

 [Chemical formula (1):

 Yes

 II

 0— C— X

 0 N 0

 II II II

 A—— C— C— C—— B

In the general formula (1), 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. Represents. BEST MODE FOR CARRYING OUT THE INVENTION

First, the photosensitive coloring composition according to the present invention will be specifically described.

The photosensitive coloring composition of the present invention contains a colorant carrier composed of a transparent resin and a precursor thereof, a colorant, and a photopolymerization initiator represented by the above general formula (1). The photopolymerization initiator represented by the general formula (1) forms a filter segment and a black matrix having an excellent pattern shape when the photosensitive coloring composition having high sensitivity contains the photopolymerization initiator. be able to.

[0020] The photopolymerization initiator represented by the general formula (1) is characterized in that α 1, α 1 -diketoxime is characterized by having a heterocyclic group or a condensed polycyclic hydrocarbon group at the 1-position and 3-position. It is an ester compound. The photopolymerization initiator used in the present invention has an absorption band from the near ultraviolet to the visible region due to the introduction of a heterocyclic group or a condensed polycyclic hydrocarbon group into Α and Β. It is possible to have activity up to a long wavelength region, 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.

[0022] The heterocyclic ring in the substituted or unsubstituted heterocyclic group represented by A or B in the general formula (1) is an aromatic group containing a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom. Examples include aliphatic heterocycles. Specific examples include 2-Chenyl group, 2-Benzoenyl group, Naphtho [2,3-b] Chenolinole group, 3 Thianthrenyl group, 2 Thianthrenyl group, 2— Furyl group, 2-benzofuryl group, biranyl group, isobenzofuranyl group, chromenyl group, xanthur group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazyl group, Pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H—indolyl group, 2 indolinole group, 3 indolinole group, 1H indazolyl group, purinyl group, 4H—key Lysinyl group, isoquinolyl group, quinolyl group, phthaladyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH force rubazolyl group, 2 force rubazolyl group, 3 force rubazolyl group, / 3-canolepolyninole group, Nantridinyl group, 2-Ataridininole group, Perimigenore group, Hue Nanto mouthlinyl group, phenazinyl group, phenazinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group Biazolidinyl group, birazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinutalidinyl group, monoleolinolinole group, thixanthryl group, 4 quinolinyl group, 4 isoquinolyl group, 3 phenothiazinyl group, 2 phenoxathinyl group Coumarinyl group, dibenzofuranyl group, coumaranyl group, 2 thiocoumarinyl group, xanthonyl group, dibenzotenyl group, thixanthuryl group, oxazolyl group, benzoxazolyl group, benzothiazolyl Group, can be exemplified 1, 4 Jichianafuchiru group, but is not limited thereto. In addition, the position where the substituted or unsubstituted heterocyclic group is bonded to the adjacent carbonyl carbon is the position of the heterocyclic group exemplified above by specifying the specific position (for example, in the 2-chenyl group). Is not limited to the 2-position, but may be any position where the heterocyclic group can be bonded to the carbonyl group next to it (for example, the Cheninore group includes 2 Chenyl, 3 Chenyl, 4 Chenyl). Or it can be 5 Cenyl.

The condensed polycyclic hydrocarbon in the substituted or unsubstituted condensed polycyclic hydrocarbon group represented by A or B in the general formula (1) is a condensed polycyclic ring formed of 7 or more carbon atoms. Specific examples include cyclic hydrocarbons such as indul, 1,3-indandionyl, naphthyl, / 3-tetralonyl, α-naphthoquinolyl, pentarenyl, azulenyl, heptaenyl, fluorenyl, and fluorenonyl. , 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, acenaphthur group , Acenaphthoquinonyl group, phenalenyl group, naphthacenyl group, chrysenyl group, pyrenyl Group, triphenylenyl group, benzo [a] anthracenyl group, benzo [a] anthraquinonyl group, aceantrirenyl group, aceanthrenyl group, aceanthrenequinolyl group, acephenanthrylenyl group, fluoranthenol group, Examples thereof include a preadenyl group, a pentacenyl group, a perylenyl group, a picenyl group, and a benzo [ _a ] pyrenyl group. Of these, ease of acquisition, ease of synthesis, etc. From the viewpoint, a condensed polycyclic hydrocarbon group in which two or three rings are condensed is preferable, but is not limited thereto. In addition, the position where the substituted or unsubstituted condensed polycyclic hydrocarbon group is bonded to the adjacent carbonyl carbon is any position as long as the condensed polycyclic hydrocarbon group can be bonded to the adjacent force sulfonyl group. Good.

 [0024] Examples of the substituent that the heterocyclic group and the condensed polycyclic hydrocarbon group described above 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. Cyclic group, acyl group, alkoxyl group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylthio group, allylthio group, heterocyclic thio group, amino group, alkylamino group, dialkylamino group, aryleno amino group, diarino Examples thereof include a reamino group, an alkylaryl amino group, a benzylamino group, and a dibenzylamino group.

 Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

 [0026] The heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And the alkyl group as a substituent includes a linear, branched or monocyclic group having 1 to 18 carbon atoms. Or a condensed polycyclic alkyl group is included. Specific examples thereof include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, Noel group, decyl group, dodecinole group, octadecyl group, isopropyl group, isobutyl group. , Isopentyl group, sec butyl group, tert butinole group, sec pentinole group, tert pentinole group, tert octinole group, neopentyl group, cyclopropyl group, cyclobutyl, cyclopentyl group, cyclohexinole group, adamantyl group, noreponorenore group, Polonyl group, 4 decylcyclohexyl group

[0027] The heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And the aryl group as a substituent includes a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms. . Specific examples thereof include, for example, phenyl group, 1 naphthyl group, 2 naphthyl group, 9 anthryl group, 9 phenanthryl group, 1-pyrenyl group, 5 naphthacenyl group, 1 induryl group, 2 azulenyl group, 1-acenaphthyl group, 9 fluorenyl group. It is a group.

[0028] The heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And the heterocyclic group as a substituent includes a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom. Ring or A condensed polycyclic heterocyclic group is included. Specific examples thereof include, for example, 2-furanyl group, 2-cenyl group, 2 indolinole group, 3 indolinole group, 2 benzofurinole group, 2 benzocenyl group, 2 rubazolyl group, 3-canolebasolinol group, 4 canolebasolinole group, 9 ataridinyl group Group

[0029] The heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And the acyl group as a substituent may be a hydrogen atom or a linear or branched chain having 1 to 18 carbon atoms; A carbonyl group to which a monocyclic or condensed polycyclic aliphatic group is bonded, or a carbonyl group to which a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms is bonded, a nitrogen atom, an oxygen atom, a sulfur atom, and And / or a carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 18 to 18 carbon atoms including a phosphorus atom is bonded, and these may have an unsaturated bond in the structure. Specific examples thereof include, for example, formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, bivaloyl group, lauroyl group, myristoyl group, nonremitinole group, stearoyl group, cyclopentylcarbonyl group, cyclohexane Hexylcarbonyl, Atalylyl, Methacryloyl, Crotonyl, Isocrotonyl, Oleoinole, Benzoyl, 2 Methylbenzoyl, 4-Methoxybenzoyl, 1 Naphthoyl, 2 Naphthoyl, Cinnamoyl, 3 Froyl Group, 2 tenol group, nicotinol group, isonicotinoyl group, 9 anthroyl group, 5-naphthaceneol group and the like.

[0030] The heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And the alkoxy group as a substituent may be a linear, branched or monocyclic group having 1 to 18 carbon atoms. Alternatively, a condensed polycyclic alkoxyl group is included. Specific examples thereof include, for example, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, iso Propoxy 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, A cyclopentyloxy group, a cyclohexyloxy group, an adamantyloxy group, a norbornyloxy group, a polonyloxy group, a 4-decylcyclohexyloxy group, a 2 tetrahydrofuranyloxy group, and a 2-tetrahydrofuranyloxy group. [0031] The aryloxy group as a substituent that the heterocyclic group and the condensed polycyclic hydrocarbon group may have includes a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms. Specific examples thereof include, for example, phenoxy group, 1 naphthyloxy group, 2-naphthyloxy group, 9 anthryloxy group, 9 phenanthryloxy group, 1-pyrenyloxy group, 5 naphthacenyloxy group, 1 induroxy group, 2-azlenenyloxy Group, 1-cenaphthyloxy group, 9-fluorenyloxy group.

 [0032] The heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And the heterocyclic oxy group as a substituent includes a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom. Monocyclic or condensed polycyclic heterocyclic oxy groups are included. Specific examples thereof include, for example, 2-furanyloxy group, 2 enyloxy group, 2 indolyloxy group, 3 indolyloxy group, 2 monobenzofuryloxy group, 2-benzozonyloxy group, 2 force rubazolyloxy group, 3 force Rubazolyloxy group, 4 rubazolyloxy group, 9 ataridinyloxy group

[0033] The heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And the acyloxy group as a substituent may be a hydrogen atom or a linear or branched chain having 1 to 18 carbon atoms; A carbonyloxy group to which a monocyclic or condensed polycyclic aliphatic group is bonded, or a carbonyloxy group to which a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms is bonded, a nitrogen atom, an oxygen atom, sulfur A carbonyloxy group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms including an atom and / or a phosphorus atom is bonded is included. Specific examples thereof include, for example, acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, bivalyloxy group, lauroyloxy group, myristyloxy group, palmitoyloxy group. Group, stearoyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, taliloyloxy group, metataryloxyloxy group, crotonoxyloxy group, isocrotonoxyloxy group, oleoyloxy group, benzoyloxy group 1 naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3 furoyloxy group, 2 tenoxyloxy group, nicotinoyloxy group, isicotinoxyloxy group, 9 anthroyloxy group, 5-naphthaceneoxyloxy group .

[0034] The heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, Alkyl as a substituent The thio group includes a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms. Specific examples thereof include, for example, methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, and octadecylthio group.

 [0035] The heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And the arylo group as a substituent includes a monocyclic or condensed polycyclic arylothio group having 6 to 18 carbon atoms. Specific examples thereof include a phenylthio group, a 1 naphthylthio group, a 2 naphthylthio group, a 9-anthrylthio group, a 9 phenanthrylthio group, and the like.

 [0036] The heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And the heterocyclic thio group as a substituent includes a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom. Monocyclic or fused polycyclic heterocyclic thio groups are included. Specific examples thereof include, for example, 2-furylthio group, 2 phenylthio group, 2 pyrrolylthio group, 6 indolylthio group, 2 benzofurylthio group, 2 benzochelylthio group, 2 force rubazolylthio group, 3 force rubazolylthio group, 4 A rubazolylthio group.

 [0037] The heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And the alkylamino group as a substituent includes, for example, a methylamino group, an ethylamino group, a propylamino group, a butylamino group, and a pentylamino group. Group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decinoreamino group, dodecylamino group, octadecinoleamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec butylamino group, tert Butylamino group, sec pentylamino group, tert pentylamino group, tertoctylamino group, neopentylamino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctyl group Amino group, cyclododecyl Amino group, 1-Adamantamino group, 2-Adamantamino group.

[0038] The heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And the dialkylamino group as a substituent includes, for example, a dimethylamino group, a jetylamino group, a dipropylamino group, a dibutylamino group, Dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, Includes methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutyramino group, cyclopropylamino group, pyrrolidino group, piperidino group, piperazino group

[0039] The heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And the arylarylamino group as a substituent includes, for example, an Narylamino group, an anilino group, a 1-naphthylamino group, and a 2-naphthylamino group. 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 Group, including p-terphenylamino group

Yes

 [0040] The heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And the diarylamino group as a substituent includes, for example, a diaryreamino group, a diphenylamino group, a ditolylamino group, N —Includes phenyl 1-naphthylamino group, N-phenyl 2-naphthylamino group.

 [0041] The heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And an alkylarylamino group as a substituent includes, for example, an N methylanilino group, an N methyl-2-pyridino group, an N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropylinole, N-pentylanilino group, N-ethylanilino group, N-methyl-1-naphthylamino group are included.

[0042] Further, the hydrogen atom of the substituent that the heterocyclic group and the condensed polycyclic hydrocarbon group may have may be further substituted with another substituent. Examples of the group include a halogen group such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group, an aryloxy group such as a phenoxy group and a p-trioxy group, and a methoxycarbonyl group. , Butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, etc., acetoxy groups, propionyloxy groups, benzyloxy groups, etc., acylyl groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups, methacryloyl groups, methoxalyl groups, etc. Alkyls such as acyl, methylsulfanyl and tert-butylsulfanyl Faniru group, Hue Nils Alpha sulfonyl group, p-tolylsulfanyl § reel sulfanyl group such as, Mechiruamino group, an alkylamino group such Kishinore amino cyclohexane, Jimechiruamino group, Jechiruamino group, a morpholino group, Pi Dialkylamino groups such as peridino group, arylamino groups such as phenylamino group, p-tolylamino group, alkyl groups such as methyl group, ethyl group, tert butyl group, dodecyl group, phenyl group, ptolyl group, xylyl group, In addition to aryl groups such as tamenyl group, naphthyl group, anthryl group, phenanthryl group, etc., hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesinole group, p-toluenesulfonyl group, amino group, nitro group Group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonyl group, dimethylsulfohumyl group, triphenylphenacylphosphonium group and the like.

 [0043] Further, a substituent structure S in A and B, another substituent, or a carbon atom on the ring may be combined to form a cyclic structure. A and B may be integrated to form a ring structure.

 [0044] Next, X in the general formula (1) represents a monovalent organic residue. The monovalent organic residue may have an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Alkynyl group, optionally substituted alkoxy group, optionally substituted aryloxy group, optionally substituted heterocyclic oxy group, optionally substituted acyloxy group, substituted An alkyl sulfanyl group that may have a group, an arylsulfanyl group that may have a substituent, an alkylsulfiel group that may have a substituent, and an arylsulfur group that may have a substituent Group, alkylsulfonyl group which may have a substituent, arylarylsulfonyl group which may have a substituent, acyl group which may have a substituent, alkoxycarbonyl group which may have a substituent A canole which may have a substituent A moyl group, a sulfamoyl group which may have a substituent, an amino group which may have a substituent, a phosphinoyl group which may have a substituent, and a heterocyclic group which may have a substituent. .

[0045] The alkyl group which may have a substituent as the monovalent organic residue is preferably an alkyl group having from 30 to 30 carbon atoms, for example, a methyl group, an ethyl group, a 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-methylsulfaurphenacinole group, 4 phenylsulfaurphenacyl group, 4-dimethylaminophenacyl group, 4 cyanophenacyl group, 4 methylphenacyl group 2, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-nitrophenacyl group, and the like.

 [0046] The aryl group that may have a substituent as the monovalent organic residue is preferably a phenyl group, a biphenyl group, a 1 naphthyl group, preferably an aryl group having 6 to 30 carbon atoms, 2-naphthinole group, 9 anthrinole group, 9 phenanthrinole group, 1-pyrenyl group, 5 naphthacenyl group, 1 indur group, 2 azulenyl group, 9 fluorenyl group, terphenyl group, quarter terphenyl group, o-, m-, And p-trinole group, xylinole group, o-, m-, and p cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quaternarynaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoro Lanturyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthrinol group, biant Cenyl group, teranthracenyl group, quarteranthra seninole group, anthraquinolinole group, phenanthrinol group, triphenylenylenole group, pyrenyl group, taricenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenylol Group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, trinaphthylenyl group, heptaphenyl group, heptaenyl group, pyrantrenyl group, and opalenyl group.

 [0047] The alkenyl group which may have a substituent as the monovalent organic residue is preferably an alkenyl group having 2 to 10 carbon atoms, such as a bur group, a allyl group, and a styryl group. Are listed.

 [0048] The monovalent organic residue may have a substituent! /, And the alkynyl group is preferably an alkynyl group having 2 to 10 carbon atoms, for example, an ethur group, a propynyl group, a propanolol group. Gill group etc. are mentioned.

[0049] The alkoxy group which may have a substituent as the monovalent organic residue is preferably an alkoxy group having 1 to 30 carbon atoms. For example, methoxy group, ethoxy group, propyloxy group, isopropyl Oxy group, butoxy group, isobutoxy group, sec butoxy group, t butoxy Group, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, dodecyloxy, octadecyloxy, ethoxycarbonylmethyl, 2-ethyl Xyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N dibutynoleaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarbonylmethyloxy group, N-methyl-N-benzylaminocarbonylmethyloxy group, benzyloxy group, cyanomethyloxy group and the like can be mentioned.

[0050] The aryloxy group which may have a substituent as the monovalent organic residue is preferably an aryloxy group having 6 to 30 carbon atoms. For example, a phenyloxy group, a 1 naphthinoreoxy group, a 2- Naphthyloxy group, 2-chlorophenyloxy group, 2-methylphenyloxy group, 2 methoxyphenyloxy group, 2 butoxyphenyloxy group, 3 chlorophenyloxy group, 3-trifluoromethylphenyloxy group , 3-cyanophenyloxy group, 3-dinitrophenyl group, 4 fluorophenyloxy group, 4 cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, Examples include 4-methylolesulfaylphenyloxy group and 4-phenylsulfaylphenyloxy group.

 [0051] The heterocyclic oxy group which may have a substituent as the monovalent organic residue is a monocyclic or condensed polyoxy group containing a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom. Specific examples include cyclic heterocyclic oxy groups such as 2-furanyloxy group, 2-phenyloxy group, 2 indoloxy group, 3 indoloxy group, 2 force rubazolyloxy group, 2 benzofuryloxy group, 2 benzocenyloxy group. Examples thereof include a xyl group, a tri-strand rubazolyloxy group, a 4-canoleverzolyloxy group, and a 9-ataridinyloxy group.

[0052] The acyloxy group which may have a substituent as the monovalent organic residue is preferably an acyloxy group having 2 to 20 carbon atoms, for example, an acetyloxy group, a propanoxy group, a butanoyloxy group, Examples include a pentanoyloxy group, a trifluoromethylcarbonyloxy group, a benzoyloxy group, a 1-naphthylcarbonyloxy group, and a 2-naphthylcarbonyloxy group. [0053] As the alkylsulfanyl group which may have a substituent as the monovalent organic residue, an alkylsulfanyl group having 1 to 20 carbon atoms is preferred, for example, a methylsulfanol group, ethyl Sulfanyl, propylsulfanyl, isopropylsulfanyl, butylsulfanyl, hexylsulfanyl, cyclohexylsulfanyl, octylsulfanyl, 2-ethylhexylsulfanyl, decanolsulfanyl, dodecanol Examples include sulfanyl group, octadecanol sulfanyl group, cyanomethylsulfanyl group, methoxymethylsulfanyl group and the like.

 [0054] As the aryl sulfanyl group which may have a substituent as the monovalent organic residue, an aryl sulfanyl group having 6 to 30 carbon atoms is preferable. For example, a phenylsulfaninole group, 1 Naphtylsulfanyl group, 2-Naphtylsulfanyl group, 2-Chlorophenylsulfanyl group, 2-Methylphenylsulfanyl group, 2-Methoxyphenylsulfanyl group, 2-Butoxyphenylsulfanyl group, 3-Chlorophenyl Sulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-diphenylsulfanyl group, 4-fluorophenylsulfanyl group, 4-cyanophenylsulfaneyl group, 4-methoxyphenyl Sulfanyl group, 4-methylsulfaylphenylsulfanyl group, 4 phenyl Alpha loose phenylsulfanyl group, and the like 4 Jimechiru § Minofu enyl sulfanyl group.

 [0055] As the above-mentioned monovalent organic residue, which may have a substituent, an alkylsulfier group having 1 to 20 carbon atoms is preferred. For example, a methylsulfier group, Tylsulfiel group, propylsulfiel group, isopropylsulfiel group, butylsulfiel group, hexylsulfiel group, cyclohexylsulfiel group, octylsulfiel group, 2-ethylhexylsulfiel group, deca Examples thereof include a neutral sulfiel group, a dodecanol sulfiel group, an octadecanol sulfiel group, a cyanomethyl sulfinyl group, and a methoxymethyl sulfier group.

[0056] As the aryl sulfiel group which may have a substituent as the monovalent organic residue, an aryl sulfiel group having 6 to 30 carbon atoms is preferable. Nore group, 1 Naphthyl sulfier group, 2-Naphthyl sulfier group, 2-Chronophenyl sulfier group, 2-Methylphenyl sulfier group, 2-Methoxyphenyl sulfier group Group, 2 butoxyphenyl sulfier group, 3 cyclophenyl sulfiel group, 3 trifluoromethylphenyl sulfinyl group, 3-cyanophenyl sulfinyl group, 3-diphenyl phenyl sulfier group, 4 Fluorophenyl sulfier group, 4-cyanophenole sulfinyl group, 4-methoxyphenyl sulfinyl group, 4-methylsulfaurenyl diresulfier group, 4-phenylsulfaylphenyl sulfier group, 4-dimethylaminophenyl sulfenyl group A Fier group etc. are mentioned.

 [0057] As the alkylsulfonyl group which may have a substituent as the monovalent organic residue, an alkylsulfonyl group having 1 to 20 carbon atoms is preferred. For example, a methylsulfonyl group, ethinoresnore Honinole group, propinolesnorehoninole group, isopropinolesnorehoninole group, butinoles nolephonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfoninole group, 2-ethylhexylsulfonyl group, decanoyl Examples thereof include a rusulfonyl group, a dodecanolylsulfonyl group, an octadecanolsulfonyl group, a cyanomethylsulfonyl group, and a methoxymethylsulfonyl group.

 [0058] The arylsulfonyl group which may have a substituent as the monovalent organic residue is preferably an arylsulfonyl group having 6 to 30 carbon atoms. For example, a phenylsulfonyl group, 1 Naphthylsulfonyl group, 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group , 3-trifluoromethenorefeninolesnorehoninole group, 3-cyanophenenolesnorehoninore group, 3-nitrophenenolesnorenorenore group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-Methoxyphenylsulfonyl group, 4-methylsulfaylphenylsulfonyl group, 4-phenylsulfaurphenyl Sulfonyl group, and 4-dimethyl § Minofu thienylsulfonyl group.

[0059] As the acyl group which may have a substituent as the monovalent organic residue, an acyl group having 2 to 20 carbon atoms is preferable. For example, an acetyl group, a propanoyl group, a butanol group, Fluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanyl benzoyl group, 4-phenylsulfanyl benzoyl group, 4-dimethylaminobenzoyl group, 4-Jetylaminobenzoyl group, 2 black mouth Benzyl group, 2-methylbenzoyl group, 2-methoxybenzoyl group, 2-butoxybenzyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-ditrobenzoyl group Group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl group and the like.

[0060] The alkoxycarbonyl group which may have a substituent as the monovalent organic residue is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, for example, a methoxycarbonyl group, ethoxy Carbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyl Oxycarbonyl group, 1 naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfurylphenyloxycarbonyl group, 4 phenylsulfanyl phenyloxycarbonyl group, 4-dimethylaminophenyl Oxycarbonyl group, 4 jetylaminophenyloxycarbonyl group, 2-carbonyl group Oral phenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenylcarbonyl group, 2 butoxyphenyloxycarbonyl group, 3 cyclophenyloxycarbonyl group, 3 trifluoro Romethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-diphenyloxycarbonyl group, 4 fluorophenyloxycarbonyl group, 4 cyanphenylcarbonyl group, 4-methoxyphenyl group and the like can be mentioned.

[0061] As the rubamoyl group which may have a substituent as the monovalent organic residue, a rubamoyl group having 1 to 30 carbon atoms is preferred. For example, N methylcarbamoyl group, N- Ethyl carbamoyl group, N propyl carbamoyl group, N butyl carbamoyl group, N hexyl carbamoyl group, N cyclohexyl carbamoyl group, N octinole carbamoyl group, N decyl carbamoyl group, N octadecyl carbamoyl group, N Rucarbamoyl group, N—2-Methylphenylcarbamoyl group, N—2—Black-opened phenylcarbamoyl group, N—2-Isopropoxyphenylcarbamoyl group, N—2- (2-ethylhexyl) phenylcarbamoyl group, N — 3 Closyl phenylcarbamoyl group, N—3—Nitrophenylcarbamoyl group, N—3—Cyanophenylcarbamoyl group Group, N—4-Methoxyphenylcarbamoyl group, N—4-Cyanophenylcarbamoyl group, N-4-methylsulfaphenylphenylcarbamoyl group, N—4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group Group, N, N dimethylenoyl ruberamoyl group, N, N dibutylcarbamoyl group, N, N diphenylcarbamoyl group and the like.

 [0062] The sulfamoyl group which may have a substituent as the monovalent organic residue is preferably a sulfamoyl group having 0 to 30 carbon atoms. For example, a sulfamoyl group, N alkynolesulfamoyl Group, N arylsulfamoyl group, N, N dialkylsulfamoyl group, N, N dialylsulfamoyl group, N-alkyl-N arylsulfamoyl group and the like. More specifically, N-methylsulfamoyl group, N-ethyl sulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfamoyl group, N-octyls norefamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2-methylpropyl Nyl-2-sulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-cyclophenylphenylsulfa Moyl group, N—3-nitrophenylsulfamoyl group, N—3-cyanophenylsulfamoyl group, N—4-methoxyphenylsulfamoyl group N-4 cyanophenylsulfamoyl group, N-4 dimethylaminophenylsulfamoyl group, N-4-methylsulfaylphenylsulfamoyl group, N-4-phenylsulfaylphenylsulfamoyl group N methyl-N phenylsulfamoyl group, N, N dimethylsulfamoyl group, N, N dibutylsulfamoyl group, N, N diphenylsulfamoyl group and the like.

[0063] The amino group which may have a substituent as the monovalent organic residue is preferably an amino group having 0 to 50 carbon atoms, for example, -NH, N-alkylamino group, Examples include N arylamino group, N acylamino group, N sulfonylamino group, N, N dialkylamino group, N, N diarylamino group, N alkyl mono-N arylamino group, N, N disulfonino amino group and the like. More specifically, an N methylamino group, an N ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-t-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group Group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino group, N-2-cyclophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2 hexylhexenole) phenylamino group, N-3 cyclophenylamine group, N-3-nitrophenylamino group, N-3-3-sianoff Nyl-3-amino group, N-3-trifluoromethylphenylamino group, N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethyl Ruphenylenylamino group, N—4-methylsulfurphenylphenylamino group, N—4-phenylsulfurphenylphenylamino 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- (dibutylcanoleboninole) amino group, N, N- (Dimethylsulfoninole) amino group, N, N- (Jetylsulfoninole) amino group, N, N— (Dibutylsulfoninole) amino group, N, N— (Diphenylsulfoninole) amino group, etc. Is mentioned.

 [0064] The phosphinoyl group which may have a substituent as the monovalent organic residue is preferably a phosphinoyl group having 2 to 50 total carbon atoms, for example, a dimethylphosphinoyl group, a dimethyl ester Phosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis ( 2, 4, 6 trimethylphenyl) phosphinoyl group and the like.

[0065] The monovalent organic residue may have a substituent! / ヽ heterocyclic group includes an aromatic or aliphatic group containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. Heterocycles are preferred. For example, Cenyl group, Benzo [b] Cenyl group, Naphth [2,3-b] Cenyl group, Thianthrenyl group, Furyl group, Biranyl group, Isobenzofuranyl group, Chromenyl group, Xanthenyl group, Phenoxathiinyl Group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H indolyl group, indolyl group, 1H indazolyl group, purinyl group, 4 H-quinolidinyl group, isoquinolyl group, quinolyl group, phthaladyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-force rubazolyl group, carbazolyl group, β Group, attaridinyl group, perimidyl group, phenanthoxylinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chrominyl group, pyrrolidinyl group, Imidazolidinyl group, imidazolininole group, virazolidinyl group, virazolinyl group, piperidinole group, piperazinyl group, indolinyl group, isoindolinyl group, quinutalidinyl group, morpholinyl group, thixanthrin And the like.

[0066] Further, the alkyl group which may have a substituent described above, an aryl group which may have a substituent, an alkenyl group which may have a substituent, and 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 acyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, and a substituent. /, Arylsulfanyl group, may have a substituent! /, Alkylsulfinyl group, arylsulfinyl group which may have a substituent, alkylsulfyl group which may have a substituent A phonyl group, an arylarylsulfonyl group which may have a substituent, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, and a force which may have a substituent Ruvamoyl group, optionally substituted sulfa The hydrogen atom of the moyl group, the amino group which may have a substituent, or the heterocyclic group which may have a substituent may be further substituted with another substituent.

[0067] Examples of such other 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, phenoxy group, p-tolyloxy group and other aryloxy groups, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl groups such as phenoxycarbonyl group, acetoxy group, propionyloxy group, and acyloxy groups such as benzoyloxy group, acetyl group, benzoyl group, Isobutyryl group, atarylloyl group, methacryloyl group, metylyl group and other isyl groups, methylsulfanyl group, alkylsulfanyl group such as tert-butylsulfanyl group, phenylsulfanyl group, and arylsulfanyl group such as p-tolylsulfanyl group, Alkylamino groups such as methylamino group, cyclohexylamino group, dimethylamino groups, dimethylolamino groups, morpholino groups, piperidino groups, etc., dialkylamino groups, phenylamino groups, p-tolylamino groups, etc., arylamino groups, methyl groups, ethyl groups, tert In addition to alkyl groups such as butyl and dodecyl groups, phenyl groups, p-tolyl groups, xylyl groups, tameyl groups, naphthyl groups, anthryl groups, phenanthryl groups, etc., hydroxy groups, carboxy groups, honoremino groups Group, mercapto group, sulfo group, mesinore group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethinole group, trimethinoresininole group, phosphinico group, phosphono group, Trimethinoleammoninolele group, dimethylsulfohumyl Group, trifylphenacylphosphoniumyl group and the like.

 [0068] X is preferably an alkyl group that may have a substituent, an aryl group that may have a substituent, an acyl group that may have a substituent, or a phosphier that may have a substituent. A heterocyclic group which may have a group or a substituent. 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 ethynole group, a propyl group, Forces including butyl group, t-butyl group, trifluoromethyl group, phenyl group, benzyl group, etc. It is not limited to these examples.

 [0069] 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.

 [0070] Further, among the photopolymerization initiators represented by the general formula (1), more preferably, A in the general formula (1) is a substituted or unsubstituted carbazolyl group, or a substituted or unsubstituted group. It is a photopolymerization initiator for naphthyl groups. 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 canolazolyl group or naphthyl group may have include the same substituents as those mentioned for the substituent that A and B may have. In addition, the partial force of the substituents on the carbazolyl group and naphthyl group is bonded to the carbon atom of the carbazolyl group or naphthyl group or a part of other substituents to form a ring structure as a unit! Moyo!

[0071] Among the photopolymerization initiators represented by the general formula (1), more preferably, A in the general formula (1) is represented by the following general formula (2), which is substituted or unsubstituted. Group or substituted or not It is a photopolymerization initiator representing a group represented by the following general formula (3). The group represented by the general formula (2) and the general formula (3) is bonded to the carbonyl carbon atom at any substitution position that can form a covalent bond with the adjacent carbonyl carbon atom. Les

 [Chemical formula 2] General formula (2):

[Chemical formula (3):

[0072] In the general formula (2), Y represents a monovalent organic residue, and examples thereof include the same monovalent organic residues as X in the general formula (1). Because of its low weight, a substituted or unsubstituted alkyl group is preferred.

 [0073] Among the photopolymerization initiators represented by the general formula (1), a group represented by the general formula (2) in which A in the general formula (1) is substituted or unsubstituted is preferable. And B is a photopolymerization initiator of the group represented by the general formula (3), which is substituted or unsubstituted.

[0074] The hydrogen atoms of the groups represented by the general formula (2) and the general formula (3) may be substituted with substituents. Examples of such substituents include A and B And the same substituents as mentioned for the substituents that may have. The substituent in formula (2) is preferably a acyl group, more preferably a substituted or unsubstituted benzoyl group or a substituted or unsubstituted alkylcarbonyl group. The specific structure of the photopolymerization initiator represented by the general formula (1) in the present invention is shown in Table 1A N. The structure of the force photopolymerization initiator is not limited thereto.

[Table 1A]

0

 II

 0— C— X

 O N O

II II II

 A― C― C― C― B

[表 m]

[Table m]

[Table 1C]

[Table id]

[Table IE]

[Table IF]

[Table 1G]

[Table 1H]

[Table 11]

[Table 1J]

[Table IK]

[Table 1L]

[Table 1M]

一般式（1)で表される光重合開始剤を合成する際の出発物質は、下記一般式 (4) で表されるようなォキシムである。 [Table IN]

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

[Chemical 4] General formula (4):

OH

 I

 0 N 0

 II II II

 A—— C—— C—— C—— B

[0076] In the general formula (4), A and B have the same meanings as A and B in the general formula (1).

 [0077] The oxime represented by the general formula (4) is, for example, Org. React., 7, 1953>, 327, edited by the Chemical Society of Japan, 4th edition, Experimental Chemistry Course, Vol. 14, p. 1316 (Maruzen) ) Can be obtained in various ways. Further, it can be obtained from a method for synthesizing oxime described in commercially available chemistry texts (for example, J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992).

 [0078] 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 Coil. Vol. VI, pp 840, Organic Syntheses Coll. Vol. III, p 191 and 51 «5, Organic ¾ynth eses Coll. 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 Suitable for the manufacture of oxime. Nitrous acid is usually produced from sodium nitrite. The nitrite alkyl ester is, for example, nitrite methyl ester, isopropyl nitrite ester, butyl nitrite ester, isoamyl nitrite ester.

 [0079] The photopolymerization initiator represented by the general formula (1) is a method described in the literature, for example, an oxime obtained by the above-described method, and a silk silk starting from the oxime represented by the general formula (4). 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. Produced by reacting.

 [0080] Such a reaction is known to those skilled in the art and is generally performed at 15 ° C to + 50 ° C, preferably 0 to 30 ° C.

[0081] All oxime ester groups exist in two configurations, (Z) or (E). Idiomatic The force by which this isomer can be separated by the method The 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.

[0083] The photopolymerization initiator represented by the general formula (1) is 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 colorant in the photosensitive coloring composition. Can be used

Yes

 [0084] In addition to the photopolymerization initiator represented by the general formula (1), other photopolymerization initiators can be used in combination with the photosensitive coloring composition of the present invention.

[0085] Other photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4 isopropylinophenenole) 2-hydroxy 2-methyl Propane 1-one, 1-hydroxycyclohexyl phenyl ketone, 2 Benzylue 2 Dimethylamino 1- (4 morpholinophenyl) Acetophenone compounds such as butane 1-on, benzoin, benzoin methyl ether, benzoin ether, benzoin Benzoin compounds such as isopropyl ether, benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methinole, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4 benzoyl 4 ' -Methyl Diph Disulfide, 3, 3 ', 4, 4'-Tetra (t-butylperoxycarbonyl) benzophenone compounds such as benzophenone, thixanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 , 4 Diisopropyl thixanthone, 2, 4 Thioxanthone compounds such as jetylthioxanthone, 2, 4, 6 trichloro-s triazine, 2 phenyl 4, 6 bis (trichloromethyl) s triazine, 2- (p methoxyphenyl) 1) 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 (trichloromethyl) 6 styryl mono s triazine, 2— (naphtho 1-yl) 4, 6 S) Triazine, 2— (4 methoxy-naphtho-1-yl) 4, 6 bis Lytrimethyl) s triazine, 2, 4 trichloromethylolene (piperonyl) 6 triazine, 2, 4 trichloromethylolene (4, -methoxystyrinole) -6 triazine and other triazine compounds, 1, 2 Octanedione, 1 1 [4 (phenylthio) 2— (1 benzoyloxime)], O (acetyl) -N- (1 phenenole 2 oxo 2 — (4'-methoxyna naphthyl) ethylidene) hydroxylamine, etc. Phosphine compounds such as oxime ester compounds, bis (2, 4, 6 trimethylbenzoinole) phenylphosphine oxide, 2, 4, 6 trimethylbenzoyl diphenylphosphine oxide, 9, 10 phenanthrenequinone Quinone compounds such as camphorquinone and ethylanthraquinone, borate compounds, strong rubazole compounds, imidazole compounds Compounds, titanocene compounds and the like. These photopolymerization initiators can be used alone or as a mixture of two or more at any ratio as required. The other photopolymerization initiator can be used in an amount of 5 200 parts by weight, preferably 10 150 parts by weight, based on 100 parts by weight of the colorant in the photosensitive coloring composition.

[0086] Furthermore, the photosensitive coloring composition of the present invention may contain a sensitizer. The sensitizer is used in an amount of 0.;! 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator in the coloring composition.

[0087] Sensitizers include unsaturated ketones represented by chalcone derivatives such as dibenzalacetone, 1,2-diketone derivatives represented by benzylyacamphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone, and the like. Derivatives, anthraquinone derivatives, xanthene derivatives, thixanthene derivatives, xanthone derivatives, thixanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, atalidine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin Conductor, tetravirazinoporphyrazine derivative, phthalocyanine derivative, tetraazaborfilazine derivative, tetraquinoxalyloborphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyllin derivative, Annulene derivatives, spiropyran derivatives, spiro Examples include xazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, and Michler's ketone derivatives.

[0088] Furthermore, Okawara Nobu et al. “Dye Handbook” (1986, Kodansha), Okawara Nobu et al. “Functional Dye Chemistry” (1981, CM1), Ikemori Tadahisa et al. “Special Function Materials” ( 1986, CMC), including, but not limited to, sensitizers. In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region is included.

 [0089] Two or more kinds of sensitizers may be used in an optional ratio as necessary.

 [0090] Among the sensitizers, examples of the sensitizer capable of particularly suitably sensitizing the photopolymerization initiator represented by the general formula (1) include thixanthone derivatives and Michler ketone derivatives. More specifically, 2, 4 Getinorethioxanthone, 2 Chlorothioxanthone, 2, 4 Diclochio thixanthone, 2 Isopropylthioxanthone, 4 Isopropylthioxanthone, 1 Chloro-4 propoxythioxanthone, 4, 4 'bis (Dimethylamino) benzophenone, 4, 4, 1-bis (jetylamino) benzophenone, 4, 4, 1-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoylru N-ethylcarbazole, 3, 6 dibenzoyl Nethylcarbazole and the like are preferably used.

 [0091] The photosensitive coloring composition of the present invention may contain an amine compound having a function of reducing dissolved oxygen.

 [0092] Examples of such amine compounds include triethanolamine, methyljetanolamine, triisopropanolamine, 4-dimethylenoreaminobenzoic acid methinole, 4-dimethylenoreaminobenzoic acid ethyl, 4-dimethylamino. Examples include isoamyl benzoate, 2 dimethylaminoethyl benzoate, 2-ethylamino 4-benzoylaminobenzoate, and N, N dimethylbalatluidine.

[0093] As described above, the colorant 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. Transparent resins include thermoplastic resins, thermosetting resins, and photosensitive resins. The precursor includes a monomer or an oligomer that is cured by irradiation with radiation to form a transparent resin, and these can be used alone or in admixture of two or more.

 [0094] 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 colorant in the coloring composition. The transparent resin precursor can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the colorant in the coloring composition.

 [0095] Examples of the thermoplastic resin include petital resin, styrene monomaleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polychlorinated butyl, chlorinated butyl-vinyl acetate copolymer, polyacetic butyl, polyurethane series. Resins, polyester resins, 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.

 [0096] The photosensitive resin has a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group in a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group (meth). A resin in which a photocrosslinkable group such as a (meth) atalyloyl group, a styryl group or the like is introduced into the polymer by reacting an acrylic compound or keihylic acid is used. In addition, a linear polymer containing an acid anhydride such as styrene maleic anhydride copolymer or 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.

[0097] Monomers and oligomers that are precursors of the transparent resin 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) Atarylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) ) Atarylate, bisphenolate A diglycidyl ether di (meth) acrylate, neopentyl tildaricol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) attaly Acrylates, ester acrylates, methylolated melamine (meth) acrylates, epoxy (meth) acrylates, urethane acrylates and other acrylic and methacrylic esters, (meth) acrylic acid, styrene, vinylol acetate, hydroxy Ethinolevinoreethenole, ethyleneglycolinoresinyl ether, pentaerythritol tribule ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-butformamide, Examples include acrylonitrile. These can be used alone or in admixture of two or more.

[0098] In the photosensitive coloring composition, the ratio M / P between the weight (P) of the transparent resin and the weight (M) of the precursor is preferably 0.10 to 1.20. 20 to 1.00 is more preferable, and 0.25 to 0.60 is particularly preferable. If the M / P force is less than 0.10, the sensitivity will be low, and if the M / P exceeds 1.20, the pattern shape will have poor linearity or tack.

Yes

 [0099] The ratio I / M between the weight (I) 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 preferred, 0.30 to 1.30 is particularly preferred.

 [0100] Further, when the photosensitive coloring composition contains a sensitizer, the ratio between the total weight (I) of the photopolymerization initiator and the sensitizer and the weight (M) of the precursor of the transparent resin I / M is 0.20 ~; 1. 50 bb

 It is preferably 0.23 to; 1.00, more preferably 0.25 to 0.60, and particularly preferably 0.25 to 0.60.

 [0101] If I / M and I / M are less than 0.20, the sensitivity is low, and I / M and I / M are 1.5 a b a b

If it exceeds 0, the pattern shape will have poor linearity.

[0102] As the colorant contained in the photosensitive coloring composition of the present invention, organic or inorganic pigments may be used alone or in admixture of two or more. Among pigments, organic pigments are usually used because pigments with high color developability and high heat resistance, particularly pigments with high heat decomposition resistance are preferred.

[0103] Specific examples of organic pigments that can be used in the photosensitive coloring composition of the present invention are as follows. Indicated by index number.

 [0104] Red photosensitive coloring compositions for forming red filter segments include, for example, C 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, Red pigments such as 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, 272, and 279 can be used. A red pigment and an orange pigment can be used in combination in the red light sensitive composition.

 [0105] Yellow photosensitive coloring compositions for forming yellow color filter segments include, for example, C 丄 Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16 , 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 6 0, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, pan, 104, 106, 108, 109, 110, 113, 1 14, 115, 116, 1 17, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 15 3, 154, 155, 156, dishes, 162, 164 , 166, 167, 168, 169, 170, 171, 172, 1 73, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc. The yellow pigment can be used.

 [0106] For the orange photosensitive coloring composition for forming the orange filter segment, for example, orange pigments such as Pigment orange 36, 43, 51, 55, 59, 61, 71, 73 are used. Touch with force S.

 [0107] For the green photosensitive coloring composition for forming the green filter segment, for example, green pigments such as C Pigment Green 7, 10, 36, and 37 can be used. A yellow pigment can be used in combination with the green photosensitive coloring composition.

 [0108] Examples of the blue photosensitive coloring composition for forming the blue filter segment include C 丄 Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22 Blue pigments such as 60, 64 and 80 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.

[0109] Examples of the cyan photosensitive coloring composition for forming the cyan filter segment include C 丄 Pigment Bluel 5: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 mag blue pigment Use with power S.

 [0110] Purple and red pigments such as Pigment Violet 1, 19, CI Pigment Red 81, 144, 146, 177, 169 are used for the magenta photosensitive coloring composition for forming the magenta color filter segment. be able to. A yellow pigment can be used in combination with the magenta photosensitive coloring composition.

 [0111] The black photosensitive coloring composition for forming the black matrix includes, for example, carbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically C pigment black 1, 6, The power S can be used with 7, 12, 20, 31 etc. A mixture of a red pigment, a blue pigment, and a green pigment can also be used for the black photosensitive coloring composition. As the black pigment, carbon black, which is preferred from the viewpoint of price and light shielding property, 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 with a black photosensitive coloring composition.

[0112] From the viewpoint of the shape of the black matrix, carbon black having a specific surface area by the BET method of 50 to 200 m ² / g is preferable. When carbon black with a specific surface area of less than 50 m ² / g is used, the black matrix shape is deteriorated. When carbon black with a specific surface area 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.

 [0113] From the viewpoint of sensitivity, carbon black having an oil absorption of 120 ml / 100 g or less of dibutyl phthalate (hereinafter referred to as “DBP”) is preferably as small as possible.

 [0114] Furthermore, the average primary particle size of carbon black is preferably 20 to 50 nm. Carbon black with an average primary particle size of less than 20 nm is difficult to disperse at a high concentration, and it is difficult to obtain a photosensitive black composition with good stability over time. This is because the black matrix shape may be deteriorated.

[0115] In addition, inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red beryllium (red iron (III) oxide), cadmium red, ultramarine blue, bituminous, chromium oxide green, cobalt Metal oxide powder such as green, amber, titanium black, synthetic iron black, titanium oxide, iron tetroxide, metal sulfide Examples include powders and metal powders. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness.

 [0116] The photosensitive coloring composition of the present invention may contain a dye within a range that does not lower the heat resistance for color matching.

 [0117] In the photosensitive coloring composition of the present invention, the coloring agent is sufficiently dispersed in the coloring agent carrier so that the dry film thickness is 0.2 to 10 m on a transparent substrate such as a glass substrate. In order to make it easy to form filter segments and black matrix by applying to the solvent, it is possible to add a solvent. Solvents include, for example, cyclohexanone, ethyl acetate sorb acetate, butyl acetate sorb acetate, 1-methoxy-2-propyl acetate, diethylene glycoresin methinore ethenore, ethino benzene, ethylene glycono lesino ethenore, xylene, ethyl ce Examples include sorb, methyl n-amyl ketone, propylene glycol monomethyl mono-tertonolene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, and petroleum solvents. These may be used alone or in combination. Use.

 [0118] The photosensitive coloring composition of the present invention comprises one or two or more colorants, together with the photopolymerization initiator, in a colorant carrier and a solvent, a three roll mill, a two roll mill, a sand mill, a kneader, It can be finely dispersed using various dispersing means such as an attritor. A photosensitive coloring composition containing two or more colorants can also be produced by mixing each colorant separately in a colorant carrier and a solvent and finely dispersing them. When the colorant is dispersed in the colorant carrier and the solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment 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 colorant carrier and a solvent using the dispersion aid. When a product is used, a color filter having excellent transparency can be obtained.

 [0119] The dispersion aid can be used in an amount of 0.;! To 40 parts by weight, preferably 0.;! To 30 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition. .

[0120] The resin-type pigment dispersant has a pigment affinity part having a property of adsorbing to the pigment and a part compatible with the colorant carrier, and adsorbs to the pigment to disperse the pigment in the colorant carrier. Cheap It works to stabilize. Specific examples of the resin-type pigment dispersant include polyurethanes, polycarboxylic acid esters such as polyatarylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkyls. Noreamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters and their modified products, amides formed by the reaction of poly (lower alkylene imines) with polyesters having free carboxyl groups And other oil-based dispersants such as (meth) acrylic acid styrene copolymer, (meth) acrylic acid (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polybulualcohol, polybulupyrrolidone, etc. Water-soluble resin, water-soluble polymer compound, polyester System, modified poly Atari rate system, an 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.

 [0121] Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, and lauryl sulfate. Monoethanolamine, trilauramine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, styrene acrylic acid copolymer monoethanolamine, polyoxyethylene alkyl Anionic surfactants such as ether phosphates; polyoxyethylene glycol ether, polyoxyethylene lauryl ether, polyoxyethylene nouryl ether, polyoxyethylene Nonionic surfactants such as ethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl quaternary ammonium salts and chaotic surfactants such as their ethylene oxide adducts; Examples include alkyl betaines such as betaine minoacetate and amphoteric surfactants such as alkyl imidazoline. These can be used alone or in admixture of two or more.

[0122] A dye derivative is a compound in which a substituent is introduced into an organic dye, and the organic dye is a light yellow aromatic polycyclic compound such as naphthalene or anthraquinone that is not generally called a dye. Is also included. Examples of the dye derivative include JP-A-63-305173 and JP-B-57. — Those described in Japanese Patent Publication No. 15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, Japanese Patent Publication No. 5-9469, etc. can be used alone or in combination of two or more. Can be used.

[0123] The photosensitive coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time of the composition, and also a silane coupling agent in order to improve adhesion to the transparent substrate. An adhesion improver such as can also be contained. Storage stabilizers include, for example, quaternary ammonium chlorides such as benzyltrimethyl chloride and jetylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butyl pyroteol, tetraethylphosphine, and tetraphenyl. Organic phosphines such as phosphine, phosphites and the like can be mentioned.

[0124] As the silane coupling agent, Byurutorisu (13 methoxyethoxy) silane, Byurueto Kishishiran, Byurushiran such as Bulle trimethoxysilane, _I - methacryloxydiethoxyphenyl Cipro built trimethoxysilane, etc. (meth) acrylic silanes, ( 3 -— (3,4 epoxy cyclohexyl)

, Β- (3,4 Epoxycyclohexenole) ethinoretriethoxysilane, β- (3,4-Epoxycyclohexenole) _{methinoretriethoxysilane} , _Ί -glycidoxypropinoletrimethoxysilane, Ί epoxysilanes such as over-glycidoxy propyl Honoré triethoxysilane, Ν- 13 (amino aminoethyl) _gamma - § amino propyl trimethoxy silane, Ν- / 3 (aminoethyl) _gamma - Aminopuro Pino Les triethoxysilane, Ν- β (Aminoethynole) γ-aminopropinoremethinolegoxysilane, Ί-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, Ν-phenolino γ-aminoprovirtrimethoxysilane, aminosilanes such as Ν phenylene Honoré one γ- Aminopurobiruto triethoxysilane, _gamma - mercaptopropyltrimethoxysilane Tokishishiran, thiosilane such such as γ- main Le mercaptopropyl triethoxy silane.

 [0125] 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 colorant in the photosensitive coloring composition. .

[0126] The photosensitive coloring composition of the present invention can be prepared in the form of a solvent development type or alkali development type colored resist material. The colored resist material is deposited in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, a monomer, a photopolymerization initiator, and a solvent. A colorant is dispersed.

 [0127] The colorant 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 the colorant carrier.

 [0128] The photosensitive coloring composition is obtained by means of centrifugation, sintered filter, membrane filter, etc.

 It is preferable to remove coarse particles of 5 μm or more, preferably coarse particles of 1 m or more, more preferably coarse particles of 0.5 μm or more and mixed dust.

 [0129] Next, the color filter of the present invention will be described.

 [0130] 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 color. A filter segment, at least one green filter segment, and at least one blue filter segment, or at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment .

 [0131] As the transparent substrate, a glass plate such as soda lime glass, low alkali borosilicate glass or non-alkali alumino borosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is 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 for driving the liquid crystal after paneling.

 [0132] The dry film thickness of the filter segment and the black matrix is preferably 0.2-2; more preferably lO ^ m, more preferably 0.2-5111. When drying the coating film, a vacuum dryer, a competition oven, an IR oven, a hot plate or the like may be used.

[0133] Formation of each color filter segment and black matrix by a photolithography method is performed by the following method. That is, a photosensitive coloring composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, or the like. Apply to 2-10111. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact or non-contact with the film. Then solvent Alternatively, the developer is not sprayed with a force immersed in an alkaline developer or sprayed.

It is possible to form a Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to a photolithography method, it is more accurate than the printing method

 In development, an aqueous solution of sodium carbonate, sodium hydroxide or the like 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.

 [0135] As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid buildup) development method, or the like can be applied.

[0136] In order to increase the UV exposure sensitivity, after applying and drying the above colored resist material, it is water-soluble! /, Is applied and dried with a water-soluble resin such as polybutyl alcohol or water-soluble acrylic resin, After forming a film that prevents the inhibition of polymerization by oxygen, UV exposure is performed.

 [0137] Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In Examples and Comparative Examples, “parts” means “parts by weight”.

First, the preparation of the acrylic resin solution and the synthesis of the photopolymerization initiator used in Examples and Comparative Examples will be described. The molecular weight of the resin is a polystyrene-equivalent weight average molecular weight measured by GPC (gel permeation chromatography).

[0139] [Preparation of acrylic resin solution]

Place 370 parts of cyclohexanone in a reaction vessel and heat to 80 ° C while injecting nitrogen gas into the vessel. At the same temperature, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, n-butyl methacrylate A polymerization reaction was carried out by adding dropwise a mixture of 55.0 parts, 2-hydroxyethyl methacrylate 15.0 parts, 2,2, monoazobisisobutyronitrile, 4.0 parts over 1 hour. After completion of the dropwise addition, the mixture was further reacted at 80 ° C for 3 hours, and then a solution in which 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone was added, and further at 80 ° C for 1 hour. The reaction was continued to obtain an acryl resin solution. [0140] After cooling to room temperature, about 2 g of the acrylic resin solution was sampled and heated and dried at 180 ° C for 20 minutes to measure the non-volatile content. Based on the measured value, the non-volatile content was added to the previously synthesized acrylic resin solution. Cyclohexanone was added so as to be 20% by weight. The obtained attalinole resin had a weight average molecular weight of 40000.

 [0141] [Synthesis of Photoinitiator A-1]

 1,3-bis (4-methoxy-naphthalene-1-inole) 25.0 parts of propane 1,3-dione are dissolved in a mixed solution of 250 parts of tetrahydrofuran and 125 parts of concentrated hydrochloric acid, and the resulting solution is stirred at room temperature. Then, 7.50 parts of tert-butyl nitrite was added dropwise over 45 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. The reaction mixture was poured into 800 parts of ice water and extracted with 750 parts of chloroform. The organic layer was washed with water (500 parts x 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-Methoxymononaphthalene 1-inore) Propane 1, 2, 3 trione 2 oxime was obtained.

 [0142] Next, 1, 3 bis (4-methoxymononaphthalene 1-inole) propane 1,2,3 trion 2-oxime 18.0 parts and sodium acetate 3.34 parts were stirred in 300 parts of benzene. To the mixture, 5.0 parts of acetic anhydride was added and heated to reflux for 4 hours. Thereafter, the reaction mixture is poured into 500 parts of ice water, the crude product is extracted with ethyl acetate, the organic layer is washed with water (300 parts x 3 times), dried over magnesium sulfate, the desiccant is filtered and the solvent is removed. After distillation, the residue was recrystallized with ethyl hexane acetate to obtain a photopolymerization initiator A-1.

 [0143] [Synthesis of Photoinitiator A-2]

 1,3-bis (4-methoxymononaphthalene 1 yl) propane 1,3-dione is changed to 1,3-bis (4 ethoxy naphthalene 1 yl) 1 propane 1 1,3-dione Except that, Photopolymerization Initiator A-2 was obtained in the same manner as Photoinitiator A-1.

 [0144] [Synthesis of Photoinitiator A-3]

 1,3-bis- (4-methoxy-naphthalene 1-yl) Propane 1,3-dione Same as photoinitiator A-1, except that 1,3-dithiophene 2-yl-propane 1,3-dione was changed. As a result, a photopolymerization initiator A-3 was obtained.

[0145] [Synthesis of photoinitiator A-4] 1,3-Bis 4-methoxy 1-naphthalene 1-inole) Photopolymerization initiator A—except that propane 1,3-dione was changed to 1 —furan 2 inole 3 thiophen 1 2 inole propane 1 1,3 dione Photopolymerization initiator A-4 was obtained in the same manner as in 1.

[0146] [Synthesis of Photoinitiator A-5]

 1,3-bis- (4-methoxy-naphthalene 1-inole) Propane 1,3-dione was changed to 1- (4-methoxy-naphthalene 1-inole) 3-thiophene 2-inolepropane 1,3-dione In the same manner as in photopolymerization initiator A-1, photopolymerization initiator A-5 was obtained.

 [0147] [Synthesis of Photoinitiator A-6]

 1,3-bis 4-methoxymononaphthalene 1-inore) Photopolymerization except that propane 1,3-dione was changed to 1 (4-methoxy-naphthalene 1-inore) 3-naphthalene 1 inolepropane 1,3-dione Photopolymerization initiator A-6 was obtained in the same manner as initiator A-1.

 [0148] [Synthesis of Photoinitiator A-7]

 1,3-bis- (4-methoxy-naphthalene 1-inole) propane 1,3-dione 1- (9-ethyl 9H-force rubazole 3-yl) 3-naphthalene 1-yl monopropan 1, Photopolymerization initiator A-7 was obtained in the same manner as photopolymerization initiator A-1, except that it was changed to 3-dione.

 [0149] [Synthesis of Photoinitiator A-8]

 1,3-Bis 4-methoxymononaphthalene 1-inole) Propane 1,3-Dione 1 1 [9 1 (2 Ethoxyethyl) -6- (2 Methyl-benzoyl) -9H Power Rubazol 3-yl] -3 — Photopolymerization initiator A-8 was obtained in the same manner as photopolymerization initiator A-1, except that it was changed to naphthalene-1-ylpropane 1,3-dione.

 [0150] The structural formula of the obtained photopolymerization initiator is shown below.

[Chemical 5]

A1I [Chemical 6]

A—6:

A

A-1 8:

[赤色顔料分散体の調製]

[Preparation of red pigment dispersion]

 Diketopyrrolopyrrole pigment (C 丄 Pigment Red 254) ("Ilga Four Red B-CF" manufactured by Chinoku 'Specialty' Chemicals) 11.0 parts, Diketopyrrolopyrrole pigment derivative 1.0 A mixture of 40.0 parts of the previously prepared acrylic resin solution and 48.0 parts of cyclohexanone was uniformly stirred and mixed, and then dispersed in an Eiger mill (Eiger Japan "Mini Model M-250 MKIIJ") for 2 hours. Thereafter, the mixture was filtered through a 5 μm filter to prepare a red pigment dispersion.

[Chemical formula 7] Diketopyro-pillar pigment derivative:

[Preparation of green pigment dispersion]

 As a pigment, a halogenated copper phthalocyanine pigment (Cment Pigment Green 36; “Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.) 7. 1 part and a monoazo pigment (C 丄 Pigment Y ellow 150; manufactured by LANXESS “E4GN — GT ”) 3. A green pigment dispersion was prepared in the same manner as the red pigment dispersion except that 9 parts were used and the pigment derivative was changed to the following triazine pigment derivative.

[Chemical 8] Triazine pigment derivatives

[Preparation of blue pigment dispersion]

 The above red pigment dispersion except that ε-type copper phthalocyanine pigment (C 丄 Pigment Blue 15: 6; BASF “Helogen Blue L 6700F”) is used as the pigment and the following phthalocyanine pigment derivative is used as the pigment derivative. A blue pigment dispersion was prepared in the same manner as the above.

 [Chemical 9] Phthalocyanine pigment derivatives

■ S

 Cu-pc; copper phthalocyanine residue

[0154] [Preparation of black pigment dispersion]

 A black pigment dispersion was prepared in the same manner as the red pigment dispersion except that 12.0 parts of carbon black (“MA77” manufactured by Mitsubishi Chemical Corporation) was used as the pigment.

[Examples 1 to 22 and Comparative Examples 1 to 4] (Preparation of photosensitive coloring composition)

 After stirring and mixing the mixture having the composition shown in Tables 2A to 2B uniformly, the mixture was filtered through a 1 μm filter to obtain each color resist material.

[Table 2A] Table 2A:

Table 2B:

¾S2 In Tables 2A-2B:

 Monomer: Trimethylolpropane tritalylate (Shin Nakamura Chemical "NK Este Nore ATMPTJ")

 Photoinitiator A: Compound A— 1

 Photoinitiator B: Compound A— 2

 Photoinitiator C: Compound A— 3

 Photoinitiator D: Compound A— 4

 Photoinitiator E: Compound A— 5

 Photoinitiator F: Compound A— 6

 Photoinitiator G: Compound A— 7

 Photoinitiator H: Compound A— 8

 Photoinitiator I: 2 Benzyl 2-dimethylamino-14 morpholinophyl) 1-butanone 1 (“Irgacure 369” manufactured by Chinoku “Specialty” Chemicals)

 Sensitization UJ: 2, 4-Detylthioxanthone The film thickness after post-baking the obtained resist material on a 10cm X 10cm glass substrate by spin coating method is as shown in Tables 3A to 3C. After coating, it was pre-beta for 15 minutes at 70 ° C in a clean oven. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Thereafter, this substrate was spray-developed using a 23 ° C. sodium carbonate aqueous solution, washed with ion-exchanged water, and air-dried. Then, post-beta for 30 minutes at 230 ° C in a clean oven,

[0156] [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 Tables 3A-3C.

[0157] (Sensitivity)

The formed filter segment or black matrix pattern The sensitivity of the resist was determined by the amount of irradiation exposure completed according to the image dimensions. The rank of evaluation is as follows.

[0158] ○: Less than 100mj / cm ²

△: 100mj / cm ² or more 300mj / cm less than ²

X: 300mj / cm ² or more

 (Pattern shape)

 The shape of the formed filter segment or black matrix pattern was evaluated by (1) pattern linearity and (2) pattern cross-sectional shape.

[0159] The linearity (1) of the pattern was evaluated by observation with an optical microscope. The rank of evaluation is as follows.

[0160] ○: Good linearity

 Δ: Partially good linearity

 X: Poor linearity

 The cross-sectional shape (2) of the pattern was evaluated by observation with a scanning electron microscope (SEM). The rank of evaluation is as follows.

[0161] ○: Forward tapered shape.

[0162] Δ: Non-tapered shape.

[0163] X: Reverse taper shape.

[0164] (Solubility evaluation)

 5 parts of the initiator was added to 100 parts of cyclohexanone, stirred with a disper, and evaluated in the following three stages.

[0165] ○: Dissolved within 5 minutes after stirring

 Δ: Dissolved between 5 and 10 minutes after stirring

 X: Not dissolved even after 10 minutes after stirring.

[Table 3A] Table 3A:

Table 3B:

[Table 3C]

表 3A〜3Cにおいて、

In Tables 3A-3C,

Film thickness: Film thickness of each color filter segment and black matrix Colorant content: Ratio of colorant based on the total solid content of the photosensitive coloring composition

M / P = (Weight of transparent resin precursor) / (Weight of acrylic resin)

 I / M = (Weight of photoinitiator) / (Weight of transparent resin precursor)

 I / M = (total weight of photopolymerization initiator and sensitizer) / (weight of transparent resin precursor). b

 [0166] As shown in Tables 3A to 3C, Examples 1 to 3 using the photopolymerization initiator represented by the general formula (1)

 The photosensitive coloring composition of 22 had high sensitivity, and the linearity and cross-sectional shape of the obtained pattern were also good. Among them, A in the general formula (1) is a group represented by the substituted or unsubstituted general formula (2), and B is a group represented by the 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 solvents.

 [0167] In contrast, the photosensitive coloring compositions of Comparative Examples 1 to 4 using other photopolymerization initiators are poor in sensitivity, pattern straightness, and cross-sectional shape. No improvement was obtained.

 [0168] As described above, the photosensitive coloring composition of the present invention has a high colorant content or forms each color filter segment and black matrix by using a specific compound as a photopolymerization initiator. Even if the film thickness is large, it is possible to form high-sensitivity and excellent color filter segments and black matrix patterns. Therefore, a high quality color filter can be obtained by using the photosensitive coloring composition of the present invention.

Claims

The scope of the claims  [1] A colorant carrier comprising a transparent resin and its precursor, a colorant, and the following general formula (1): —General formula (1):  0  II  〇 One C— X 0 N 0  II II II  A—— C—— C— C— B (Wherein, 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). A photosensitive coloring composition containing a photopolymerization initiator.  [2] The ratio (M / P) of the weight of transparent resin (P) to the weight of transparent resin precursor (M) is 0. 10 1. The photosensitive coloring composition according to claim 1, which is 1.20. [3] Ratio (I / M) force between the weight of photopolymerization initiator (I) and the weight of transparent resin precursor (M) 0 The photosensitive coloring composition according to claim 1, which is 20 to; 1.50. [4] Further containing a sensitizer, the total weight (I) of the photopolymerization initiator and the sensitizer, and a precursor of the transparent resin  b  2. The photosensitive coating according to claim 1, wherein the ratio (I / M) to the weight (M) is 0.20 to 1.50.  b  Color composition.  [5] A color filter comprising a filter segment formed from the photosensitive coloring composition according to claim 1 on a transparent substrate. [6] A color filter comprising a black matrix formed from the photosensitive coloring composition according to any one of claims;! To 4 on a transparent substrate.