JP5496482B2 - Novel compound, photopolymerizable composition, photopolymerizable composition for color filter, color filter and method for producing the same, solid-state imaging device, and lithographic printing plate precursor - Google Patents

Description

  The present invention relates to a novel oxime compound, a photopolymerizable composition, a photopolymerizable composition for a color filter, a color filter, a method for producing the same, a solid-state imaging device, and a lithographic printing plate precursor.

Examples of the photopolymerizable composition include those obtained by adding a photopolymerization initiator to a polymerizable compound having an ethylenically unsaturated bond. Since such a photopolymerizable composition is polymerized and cured when irradiated with light, it is used in photocurable inks, photosensitive printing plates, color filters, various photoresists, and the like.
Moreover, as a photopolymerizable composition, there exists another aspect which generate | occur | produces an acid by irradiation of light, for example, and uses the generated acid as a catalyst. Specifically, it is used as a material for image formation, anti-counterfeiting, detection of energy dose by utilizing the coloring reaction of the dye precursor with the generated acid as a catalyst, or the decomposition reaction with the generated acid as a catalyst. Is used for positive resists for semiconductor manufacturing, TFT manufacturing, color filter manufacturing, micromachine component manufacturing, etc.

  In recent years, photopolymerizable compositions that are particularly sensitive to light sources of short wavelengths (365 nm and 405 nm) have been desired for various applications, and compounds exhibiting excellent sensitivity to such short wavelength light sources, for example, There is an increasing demand for photopolymerization initiators. However, since a photopolymerization initiator having excellent sensitivity generally lacks stability, a photopolymerization initiator that satisfies the improvement in sensitivity and the stability over time is desired.

Therefore, oxime ester derivatives are proposed in the following Patent Documents 1 to 4 as photopolymerization initiators used in the photopolymerizable composition. However, these known oxime ester compounds have not yet been satisfactory in terms of sensitivity because of their low absorbance at wavelengths of 365 nm and 405 nm.
Moreover, the present situation is that a photopolymerizable composition having excellent sensitivity to light with a short wavelength such as 365 nm and 405 nm is desired as well as excellent temporal stability.
Furthermore, for example, Patent Document 5 discloses a colored radiation-sensitive composition for a color filter containing an oxime compound, but the stability over time and the sensitivity to light with a short wavelength are still insufficient. there were. Moreover, in the colored radiation-sensitive composition for color filters, the reproducibility of the hue after pattern formation has become a new problem, and improvement of the problem that the colorability changes with time has been strongly desired.

On the other hand, a color filter for an image sensor has a strong demand for a high color density and a thin film of the color filter in order to improve image quality due to high light condensing property and high color separation of a solid-state imaging device such as a CCD. When a large amount of coloring material is added to obtain a high coloring density, the sensitivity is insufficient to faithfully reproduce the shape of a fine pixel pattern of 2.5 μm or less, and overall pattern loss tends to occur frequently. There is. In order to eliminate this loss, it is necessary to irradiate light with higher energy, so that the exposure time becomes longer and the manufacturing yield is significantly reduced. From the above, the colored radiation-sensitive composition for color filters has high sensitivity because it is necessary to obtain good pattern formability while containing a colorant (colorant) at a high concentration. It is the present situation that this is desired.
US Pat. No. 4,255,513 US Pat. No. 4,590,145 JP 2000-80068 A JP 2001-233842 A JP 2006-195425 A

A first object of the present invention is to provide a photopolymerizable composition capable of forming a cured film that has high sensitivity to light having a wavelength of 365 nm or 405 nm, is excellent in stability over time, and can further suppress coloring over time. An object of the present invention is to provide a novel oxime compound that is suitably used in a photopolymerizable composition.
The second object of the present invention is photopolymerization for a color filter, which has excellent temporal stability, is cured with high sensitivity, has good pattern-forming properties, and can form a colored pattern with excellent adhesion to a support. It is to provide a sex composition.
Furthermore, a third object of the present invention is to provide a color filter comprising a colored pattern having a good pattern shape and excellent adhesion to a support, using the photopolymerizable composition for a color filter, and Another object of the present invention is to provide a manufacturing method capable of manufacturing the color filter with high productivity, and further to provide a solid-state imaging device including the color filter.
In addition, a fourth object of the present invention is to provide a lithographic printing plate precursor having high sensitivity, excellent temporal stability and printing durability, using the photopolymerizable composition for a photosensitive layer. .

As a result of intensive studies, the present inventors have found that by using an oxime compound having a novel structure, it has a good absorbance with respect to light having a wavelength of 365 nm or 405 nm, and is excellent in stability over time. Obtained. Specific means for solving the above problems will be described below.
That is, the invention according to claim 1 is a novel oxime compound represented by the following general formula ( 2 ).

In the general formula ( 2 ), R represents an acyl group, X represents an alkyl group , A represents an unsubstituted alkylene group, Y represents Y1 or Y2 below, Ar represents an unsubstituted phenyl group, alkyl A phenyl group substituted with a group or a phenyl group substituted with a halogen is represented. n is an integer of 0-2.

The invention according to claim 2 is the novel oxime compound according to claim 1, which is a compound represented by the following general formula (3).

In the general formula (3), R represents an acyl group, X represents an alkyl group, A represents an unsubstituted alkylene group, Ar represents an unsubstituted phenyl group, a phenyl group substituted with an alkyl group, or Represents a phenyl group substituted with halogen. n is an integer of 0-2.

The invention according to claim 3 is the general formula (2) or (3), wherein R is an acetyl group, X is a methyl group, Ar is an unsubstituted phenyl group, or a phenyl group substituted with a methyl group. Or a novel oxime compound according to claim 1 or 2, which represents a phenyl group substituted with Cl or Br.
The invention according to claim 4 is the general formula (2) or (3), wherein A is —CH. ₂ CH ₂ It is-, It is a novel oxime compound of any one of Claims 1-3 characterized by the above-mentioned.

The invention according to claim 5 is the novel oxime compound according to claim 1, wherein the compound represented by the general formula (2) is any one of compounds 1 to 6 described later.

The invention according to claim 6 is a photopolymerizable composition comprising (A) the novel oxime compound according to any one of claims 1 to 5 and (B) a polymerizable compound. It is.

The invention according to claim 7 is a photopolymerizable composition according to claim 6, characterized by further containing (C) a colorant.
The invention according to claim 8 is the photopolymerizable composition according to claim 7, characterized in that (C) the colorant is a pigment and (D) further contains a pigment dispersant.
The invention according to claim 9 is the photopolymerizable composition according to claim 7 or 8 , wherein the colorant (C) is a black colorant.

The invention according to claim 10 is a photopolymerizable composition for a color filter, comprising the photopolymerizable composition according to any one of claims 7 to 9 .
The invention according to an eleventh aspect is a color filter having a colored pattern formed using the photopolymerizable composition for a color filter according to the tenth aspect on a support.
The invention according to claim 1 2, on a support, forming a photopolymerizable composition layer by applying a color filter photopolymerizable composition according to claim 10, wherein the photopolymerizable composition A method for producing a color filter, comprising: exposing a layer through a mask; and developing the photopolymerizable composition layer after exposure to form a colored pattern.
The invention according to claim 1 3, which is a solid-state imaging device, comprising the color filter according to claim 11.

Invention comprises a support, a photopolymerizable composition according to claim 6, i.e., containing the compound and a polymerizable compound represented by the above general formula (2) or (3) according to claim 1 4 A lithographic printing plate precursor comprising a photosensitive layer containing a photopolymerizable composition.

According to the present invention, a photopolymerizable composition capable of forming a cured film having high sensitivity to light with a wavelength of 365 nm or 405 nm, excellent stability over time, and further capable of suppressing coloration due to heating over time, and the photopolymerizability. The novel oxime compound used suitably for a composition can be provided.
In addition, according to the present invention, the photopolymerizability for a color filter is excellent in stability over time, cured with high sensitivity, has good pattern forming properties, and can form a colored pattern with excellent adhesion to a support. A composition can be provided.
Furthermore, according to the present invention, a color filter comprising the above-mentioned photopolymerizable composition for a color filter, having a good pattern shape and a colored pattern having excellent adhesion to a support, and the color A manufacturing method capable of manufacturing a filter with high productivity, and further, a solid-state imaging device including the color filter can be provided.
In addition, according to the present invention, it is possible to provide a lithographic printing plate precursor having high sensitivity, excellent temporal stability and printing durability, using the photopolymerizable composition for a photosensitive layer.

<New oxime compound>
The novel oxime compound of the present invention is a compound represented by the following general formula (2) among the compounds represented by the following general formula (1) (hereinafter referred to as “new oxime compound” as appropriate). is there.

  In the general formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group shown below.
Examples of the monovalent nonmetallic atomic group represented by R include an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An alkynyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent An arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, and a substituent. Good phosphinoyl group, heterocyclic group which may have a substituent, alkylthiocarbonyl group which may have a substituent, arylthiocarbonyl group which may have a substituent, dialkyl which may have a substituent Aminocal Group, optionally dialkylaminothiocarbonyl group, or the like may have a substituent.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group , 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-nitro Enashiru group, and the like.

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

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

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

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, such as a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfuric group Iniru group, 4-dimethylaminophenyl sulfinyl group and the like.

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

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminopheny Sulfonyl group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyl. Examples thereof include an oxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  The aryloxycarbonyl group which may have a substituent includes a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenyloxycarbonyl group, and a 4-phenylsulfanylphenyloxycarbonyl group. 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3 -Chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fur B phenyloxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and 4-methoxyphenyloxycarbonyl group.

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

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

  Examples of the alkylthiocarbonyl group which may have a substituent include, for example, methylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, hexylthiocarbonyl group, octylthiocarbonyl group, decylthiocarbonyl group, octadecylthiocarbonyl group, Examples thereof include a trifluoromethylthiocarbonyl group.

  Examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, 4-dimethyl. Aminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group Group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group Boniru group, 4-methoxyphenyl thiocarbonyl group.

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

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

  Among them, from the viewpoint of increasing sensitivity, R is more preferably an acyl group, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable.

Examples of the monovalent substituent represented by B include an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an arylcarbonyl group which may have a substituent, or Represents a heterocyclic carbonyl group which may have a substituent. Among them, the structure shown below is particularly preferable.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in General Formula (2), which will be described later, and preferred examples are also the same.

Examples of the divalent organic group represented by A include alkylene having 1 to 12 carbon atoms which may have a substituent, cyclohexylene which may have a substituent, and alkynylene which may have a substituent. Is mentioned.
Examples of the substituent that can be introduced into these groups 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- Aryloxy groups such as tolyloxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acyloxy groups such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group Group, acyl group such as methacryloyl group, methoxalyl group, methylsulfanyl group, alkylsulfanyl group such as tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, Alkylamino groups such as hexylamino group, dimethylamino groups, diethylamino groups, morpholino groups, dialkylamino groups such as piperidino groups, phenylamino groups, arylamino groups such as p-tolylamino groups, methyl groups, ethyl groups, tert- In addition to alkyl groups such as butyl group and dodecyl group, phenyl groups, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group and the like, hydroxy group, carboxy group, formyl group, mercapto Group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfonyl group Group, triphenylphenacylphos Niumiru group, and the like.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent.
Specifically, phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, pentalenyl group, binaphthalenyl group, Turnaphthalenyl group, Quarter naphthalenyl group, Heptaenyl group, Biphenylenyl group, Indacenyl group, Fluoranthenyl group, Acenaphthylenyl group, Aceantrirenyl group, Phenalenyl group, Fluorenyl group, Anthryl group, Bianthracenyl group, Teranthracenyl group, Quarter Anthracenyl group, anthraquinolyl group, phenanthri Group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, A trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, an obalenyl group, and the like can be given. Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  When the phenyl group has a substituent, examples of the substituent include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group. Group, aryloxy group such as phenoxy group, p-tolyloxy group, methylthioxy group, ethylthioxy group, alkylthioxy group such as tert-butylthioxy group, arylthiooxy group such as phenylthioxy group, p-tolyloxy group, methoxycarbonyl Groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups, benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups, methacryloyl groups, methoxalyl groups, etc. Group, Alkylsulfanyl groups such as tilsulfanyl group, tert-butylsulfanyl group, arylsulfanyl groups such as phenylsulfanyl group, p-tolylsulfanyl group, alkylamino groups such as methylamino group, cyclohexylamino group, dimethylamino group, diethylamino group, Dialkylamino groups such as morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, alkyl groups such as ethyl group, tert-butyl group and dodecyl group, hydroxy group, carboxy group, formyl group, mercapto Group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, di Chill sulfo Niu mill group, triphenyl phenacyl phosphonium Niu mill group, and the like.

  In the general formula (1), it is preferable from the viewpoint of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure.

Novel oxime compound of the invention, I compound der represented by the following general formula (2), among which, R represents an acyl group, X represents an alkyl group, A represents an unsubstituted alkylene group Y represents Y1 or Y2, Ar represents a phenyl group substituted with an unsubstituted phenyl group, an alkyl group, or a phenyl group substituted with a halogen, and n is a compound having an integer of 0-2. .

  In the general formula (2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, and Ar represents an aryl group. n is an integer of 0-5.

  R, A, and Ar in the general formula (2) have the same meanings as R, A, and Ar in the general formula (1), and preferred examples thereof are also the same.

  Examples of the monovalent substituent represented by X include an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkenyl group that may have a substituent, and a substituent. An alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, and a substituent. Good arylthioxy group, acyloxy group which may have a substituent, alkylsulfanyl group which may have a substituent, arylsulfanyl group which may have a substituent, alkyl which may have a substituent A sulfinyl group, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, May have a substituent An alkoxycarbonyl group, an optionally substituted carbamoyl group, an optionally substituted sulfamoyl group, an optionally substituted amino group, an optionally substituted phosphinoyl group, and a substituent A heterocyclic group, a halogen group and the like which may have

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-ni Rofenashiru group, and the like.

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

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, for example, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, or a sec-butoxy group. Tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, ethoxycarbonylmethyl group, 2 -Ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarb Methylpropenylmethyl group, N- methyl -N- benzylaminocarbonyl methyloxy group, a benzyloxy group, and a cyanomethyloxy group.

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

  The alkylthioxy group which may have a substituent is preferably a thioalkoxy group having 1 to 30 carbon atoms. For example, a methylthioxy group, an ethylthioxy group, a propylthioxy group, an isopropylthioxy group, a butylthioxy group, an isobutylthio group. Oxy group, sec-butylthioxy group, tert-butylthioxy group, pentylthioxy group, isopentylthioxy group, hexylthioxoxy, heptylthioxy group, octylthioxy group, 2-ethylhexylthioxy group, decylthioxy group, dodecylchioxy group Examples thereof include an oxy group, an octadecylthioxy group, and a benzylthioxy group.

  The arylthioxy group which may have a substituent is preferably an arylthioxy group having 6 to 30 carbon atoms, such as a phenylthioxy group, a 1-naphthylthioxy group, a 2-naphthylthioxy group, 2 -Chlorophenylthioxy group, 2-methylphenylthioxy group, 2-methoxyphenylthioxy group, 2-butoxyphenylthioxy group, 3-chlorophenylthioxy group, 3-trifluoromethylphenylthioxy group, 3-cyano Phenylthioxy group, 3-nitrophenylthioxy group, 4-fluorophenylthioxy group, 4-cyanophenylthioxy group, 4-methoxyphenylthioxy group, 4-dimethylaminophenylthioxy group, 4-methylsulfanyl Examples thereof include a phenylthioxy group and a 4-phenylsulfanylphenylthioxy group.

  The acyloxy group which may have a substituent is preferably an acyloxy group having 2 to 20 carbon atoms, such as an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, or trifluoromethylcarbonyloxy. Group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

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

  The arylsulfanyl group which may have a substituent is preferably an arylsulfanyl group having 6 to 30 carbon atoms, such as a phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, 2-chlorophenylsulfanyl group, 2-methylphenylsulfanyl group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group, 4-fluorophenylsulfanyl group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfuric group Aniru group, 4-dimethylamino-phenylsulfanyl group and the like.

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

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, such as a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfuric group Iniru group, 4-dimethylaminophenyl sulfinyl group and the like.

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

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminopheny Sulfonyl group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyl. Oxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4- Phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group Group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group , 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group and the like.

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

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

The amino group which may have a substituent is preferably an amino group having 0 to 50 carbon atoms in total, for example, —NH ₂ , N-alkylamino group, N-arylamino group, N-acylamino group, N— Examples include sulfonylamino group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group and the like. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-tert-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenyla Group, N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino Group, N-4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenyl Amino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) Amino group, N, N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group, morpholino group, 3, - dimethyl morpholino group, and a carbazolyl group.

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

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

  Examples of the halogen group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Furthermore, the alkyl group which may have a substituent mentioned above, the aryl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, a substituent An alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylthioxy group that may have a substituent, an arylthioxy group that may have a substituent, and a substituent. An acyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, an arylsulfanyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, and a substituent. Good arylsulfinyl group, alkylsulfonyl group which may have a substituent, arylsulfonyl group which may have a substituent, acyl group which may have a substituent, alkoxycarbonyl which may have a substituent Base The carbamoyl group which may have a substituent, the sulfamoyl group which may have a substituent, the amino group which may have a substituent, and the heterocyclic group which may have a substituent may be further substituted. It may be substituted with a group.

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

Among these, X has an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy which may have a substituent A group, an arylthioxy group which may have a substituent, and an amino group which may have a substituent are preferable.
Moreover, although n in General formula (2) represents the integer of 0-5, the integer of 0-2 is preferable.

  Examples of the divalent organic group represented by Y include the structures shown below. In the group shown below, “*” represents a bonding position between Y and an adjacent carbon atom in the general formula (2).

  Among these, from the viewpoint of increasing sensitivity, the following structures are preferable.

  The novel oxime compound of the present invention is preferably a compound represented by the following general formula (3).

  In the general formula (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 0-5.

  R, X, A, Ar, and n in the general formula (3) have the same meanings as R, X, A, Ar, and n in the general formula (2), and preferred examples are also the same.

Specific examples of the compound represented by the general formula (1) ( including the novel oxime compound of the present invention ) are shown below, but the present invention is not limited thereto.

The novel oxime compound of the present invention has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm. More preferably, a material having an absorption wavelength in a wavelength region of 360 nm to 480 nm can be exemplified. In particular, those having high absorbance at 365 nm and 455 nm are preferable.
Thus, the novel oxime compound has absorption in a long wavelength region as compared with the conventional oxime compound. Therefore, when exposed with a light source of 365 nm or 405 nm, excellent sensitivity is exhibited.

In the novel oxime compound of the present invention, the molar extinction coefficient at 365 nm or 405 nm is preferably 10,000 to 300,000, more preferably 15,000 to 300,000, and more preferably 20,000 to 200,000 from the viewpoint of sensitivity. Particularly preferred.
Here, the molar extinction coefficient of the novel oxime compound was measured with a UV-visible spectrophotometer (Carry-5 spectrophotometer manufactured by Varian) at a concentration of 0.01 g / L using an ethyl acetate solvent.

  Although the novel oxime compound of this invention is compoundable by the method shown below, for example, it is not limited to this method.

Content of the novel oxime compound in the photopolymerizable composition of this invention is 0.1-30 mass% in the total solid of a photopolymerizable composition, 1-25 mass% is more preferable, 2-20 Mass% is particularly preferred.
A novel oxime compound may be used individually by 1 type, and may use 2 or more types together.

The novel oxime compound of the present invention has a function as a photopolymerization initiator that is decomposed by light and initiates and accelerates polymerization of a polymerizable compound. In particular, since the novel oxime compound has excellent sensitivity to a 365 nm or 405 nm light source, it exhibits excellent effects when used as a photopolymerization initiator in a photopolymerizable composition.
Moreover, the novel oxime compound of this invention is applicable also to the use shown below.
That is, for example, for printing inks, for example for screen printing inks, for offset or flexographic printing inks, for UV curable inks, for example for white or colored finishes on wood or metal, for powder coatings, in particular for paper It can be developed with organic solvents or aqueous alkali for coating materials for wood, metal or plastic, for marking buildings, for road marking, for photographic reproduction techniques, for holographic recording materials, for image recording techniques For the production of printing masters, for sun curable coatings for the production of screen printing masks, for dental filling compositions, for adhesives, for pressure sensitive adhesives, for laminating resins, liquids and As an etching resist for both dry thin films, For resists, for electroplating resists or permanent resists, for optical component dielectrics for printed circuit boards and electronic circuits, for various displays, for optical switches, for optical gratings (interference gratings) For the production of optical circuits, for mass production (UV curing with transparent molds) or for the production of three-dimensional articles by stereolithographic techniques (for example as described in US Pat. No. 4,575,330) Electronic components and integrated circuits for the production of composite materials (eg, styrenic polyesters that may contain glass fibers and / or other fibers and other auxiliaries, if desired) and other thick layer compositions. For resists for coating or sealing, or for optical fibers, or optical lenses, eg contact lenses or Fresnel For coatings for the manufacture of medical devices, further for the production of medical devices, aids or implants, for example as described in German Patent No. 19,700,064 and European Patent No. 678,534 Various uses for the production of gel having properties can be mentioned.

  In addition, the novel oxime compound of the present invention can generate an acid upon irradiation with energy rays, particularly light. Therefore, it can be applied to other uses that use the generated acid as a catalyst. Specifically, image formation using a coloring reaction of a dye precursor using the generated acid as a catalyst, forgery prevention, energy dose It can also be used for materials for detection, as well as positive resists for semiconductor manufacturing, TFT manufacturing, color filter manufacturing, micromachine component manufacturing, etc. using a decomposition reaction catalyzed by the generated acid. .

  As described above, since the novel oxime compound of the present invention can be used as a photopolymerization initiator, it can be used together with the polymerizable compound to be polymerized and cured by light (the photopolymerization of the present invention). It is preferable to apply to the composition.

<Photopolymerizable composition>
The photopolymerizable composition of the present invention is characterized by containing the above-mentioned (A) novel oxime compound and (B) polymerizable compound.
The photopolymerizable composition of the present invention has high sensitivity to light having a wavelength of 365 nm or 405 nm, is excellent in stability over time, and can form a cured film that can suppress coloring due to heating over time. Although the detailed mechanism is unknown, the new oxime compound has a structure that absorbs light and suppresses radical recombination when cleaved, so that the amount of generated radicals is large and high sensitivity can be achieved. . Moreover, from the point that radical recombination is suppressed, it is considered that the reaction between the decomposition products of the novel oxime compound is suppressed during heating and the coloring resulting from the reaction is suppressed.

In the present invention, the color difference ΔEab ^* may be used to evaluate the coloration of the cured film over time. Here, the color difference ΔEab ^* can be measured with MCPD-3000 manufactured by Otsuka Electronics Co., Ltd.
As conditions for the evaluation, first, the photopolymerizable composition of the present invention is applied to an ultra-high pressure mercury lamp proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) or an i-line stepper exposure apparatus FPA-3000i5 + (Canon). Ltd.) (exposed with various exposure amount range 365 nm) of ^{10mJ / cm 2 ~2500mJ / cm 2} , to form a cured film. Then, after developing as desired, the cured film is heated at 200 ° C. for 1 hour.
By measuring the color difference ΔEab ^* before and after heating of the cured film, the colored state of the cured film over time can be evaluated.
According to the photopolymerizable composition of the present invention, the color difference ΔEab ^* before and after heating can be made 5 or less.

  The photopolymerizable composition of the present invention includes a molding resin, a casting resin, a resin for optical modeling, a sealant, a dental polymerization material, a printing ink, a paint, a photosensitive resin for a printing plate, a color proof for printing, and a color filter. Photopolymerizable composition, black matrix resist, printed circuit board resist, semiconductor manufacturing resist, microelectronics resist, micromachine component manufacturing resist, etc., insulating material, hologram material, waveguide material, overcoat agent, It can utilize for various uses, such as an adhesive agent, an adhesive, an adhesive agent, and a peeling coating agent.

  The photopolymerizable composition of the present invention is a photopolymerizable composition (1) that can be suitably used for forming a color filter, and a photopolymerizable composition that can be suitably used for forming a photosensitive layer of a lithographic printing plate precursor. The composition (2) will be described as an example, but the photopolymerizable composition of the present invention is not limited to these.

-Photopolymerizable composition (1)-
[(1)-(A) Novel oxime compound]
The (A) novel oxime compound contained in the photopolymerizable composition (1) can function as a polymerization initiator in the composition.
The content of the novel oxime compound in the photopolymerizable composition (1) is preferably 0.5 to 40% by mass, more preferably 1 to 35% by mass, and more preferably 1.5 to 30% with respect to the total solid content of the composition. More preferred is mass%.

The photopolymerizable composition (1) may be used in combination with a known photopolymerization initiator other than the novel oxime compound as long as the effects of the present invention are not impaired.
The photopolymerization initiator that can be used in combination is a compound that is decomposed by light and starts and accelerates polymerization of a polymerizable compound described later, and preferably has absorption in a wavelength region of 300 to 500 nm. Specifically, for example, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, biimidazole compounds Organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

[(1)-(B) polymerizable compound]
The polymerizable compound that can be used in the photopolymerizable composition (1) is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and preferably has at least one terminal ethylenically unsaturated bond, preferably It is selected from compounds having two or more. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (A)
(However, in general formula (A), R ⁴ and R ⁵ each represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, the Japan Adhesion Association magazine vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these addition polymerizable compounds, the details of usage, such as the structure, single use or combination, addition amount, etc., can be arbitrarily set according to the final performance design of the photopolymerizable composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.
Also, it is addition-polymerizable with respect to compatibility and dispersibility with other components (for example, photopolymerization initiator, colorant (pigment, dye), binder polymer, etc.) contained in the photopolymerizable composition. The selection and use method of the compound is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more compounds in combination. In addition, a specific structure may be selected for the purpose of improving adhesion to a hard surface such as a support.

[(1)-(C) Colorant]
The photopolymerizable composition (1) can contain a colorant (C). By containing a colorant, a colored photopolymerizable composition having a desired color can be obtained.
In addition, since the photopolymerizable composition (1) contains a novel oxime compound (A) having excellent sensitivity to a 365 nm or 406 nm light source which is a short wavelength light source, it contains a colorant at a high concentration. Can be cured with high sensitivity.

  The colorant used in the photopolymerizable composition (1) is not particularly limited, and various conventionally known dyes and pigments can be used singly or in combination, and these are photopolymerizable. It is suitably selected according to the use of the composition. When the curable coloring composition of the present invention is used for producing a color filter, it is generally used for forming chromatic colorants such as R, G, and B that form color pixels of a color filter, and a black matrix. Any black colorant can be used.

Hereinafter, the colorant that can be applied to the photopolymerizable composition (1) will be described in detail by taking a colorant suitable for color filter use as an example.
As the chromatic pigment, various conventionally known inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a fine one as much as possible, and considering the handling properties, the average particle diameter of the pigment is 0.01 μm to 0.1 μm is preferable, and 0.01 μm to 0.05 μm is more preferable.

  Examples of inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And metal oxides of the above metals.

As an organic pigment, for example,
C. I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1, 7;
Examples thereof include carbon black.

  In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These pigments having a basic N atom exhibit good dispersibility in the photopolymerizable composition (1). Although the cause is not fully elucidated, it is presumed that the good affinity between the photosensitive polymerization component and the pigment has an influence.

  Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Black 1

  These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment , Etc. can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Mixing with CI Pigment Yellow 139 is preferred. The mass ratio of the yellow pigment to the red pigment (yellow pigment / red pigment) is preferably 5/100 to 50/100. If it is less than 5/100, it is difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be increased. On the other hand, if it exceeds 50/100, the dominant wavelength becomes shorter and the deviation from the NTSC target hue may become large. In particular, the mass ratio is optimally in the range of 10/100 to 30/100. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixture with CI Pigment Yellow 185 is preferred. The mass ratio of the yellow pigment to the green pigment (yellow pigment / green pigment) is preferably in the range of 5/100 to 150/100. If the mass ratio is less than 5/100, it is difficult to suppress the light transmittance of 400 nm to 450 nm, and the color purity may not be increased. On the other hand, if it exceeds 150/100, the dominant wavelength becomes longer and the deviation from the NTSC target hue may become large. The mass ratio is particularly preferably in the range of 30/100 to 120/100.

  As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment Blue 15: 6 and C.I. I. Mixing with Pigment Violet 23 is preferred. The mass ratio of purple pigment to blue pigment (purple pigment / blue pigment) is preferably in the range of 0/100 to 30/100, more preferably 10/100 or less.

Moreover, when using the photopolymerizable composition (1) when forming a black film such as a black matrix, a black one (black colorant) is used as the colorant.
In the present invention, as the black colorant, various known black pigments and black dyes can be used. In particular, from the viewpoint of realizing a high optical density in a small amount, carbon black, titanium black, titanium oxide, iron oxide, Manganese oxide, graphite and the like are preferable, and among them, it is preferable to include at least one of carbon black and titanium black.
These black colorants may be used alone or in combination of two or more.

  The average particle diameter (average primary particle diameter) of the black pigment is preferably small from the viewpoint of residue control during development, and specifically, preferably 30 nm or less. Among these, in order to suppress residues during development when producing a color filter that requires high resolution, the average primary particle size (particle size) is preferably 5 nm to 25 nm, more preferably 5 nm to 20 nm, and more preferably 5 nm to 15 nm. The following are particularly preferred:

The content of the black colorant in the total solid content of the photopolymerizable composition (1) is not particularly limited, but is preferably as high as possible in order to obtain a high optical density with a thin film, and is 25% by mass. -80 mass% is preferable, 30 mass%-75 mass% is still more preferable, and 35 mass%-70 mass% is especially preferable.
If the amount of black colorant is too small, it is necessary to increase the film thickness in order to obtain a high optical density. If the amount of black colorant is too large, photocuring will not proceed sufficiently and the strength of the film will be reduced, or during alkali development. However, the development latitude tends to be narrow.

  In the photopolymerizable composition (1), a plurality of black colorants may be used in combination. In this way, when a plurality of black colorants are used in combination and carbon black is used as the main component, the mass ratio is in the range of carbon black: black colorant used in combination = 95: 5 to 60:40. Preferably, 95: 5-70: 30 is more preferable, and 90: 10-80: 20 is still more preferable. The mass of the black colorant used in combination is the total mass thereof. By setting the mass ratio of the black colorant used in combination with the carbon black in the range of 95: 5 to 60:40, a stable coating film without aggregation and unevenness in the photopolymerizable composition (1) can be obtained. It tends to be created.

  Examples of the carbon black suitable for the present invention include carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 900 manufactured by Mitsubishi Chemical Corporation. 850, MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Rack N339, Diamond Black SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LP Carbon black thermax N990, N991, N907, N908, N990, N991, N908 manufactured by Cancarb; Carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # manufactured by Asahi Carbon 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal; Degussa Carbon Black Color Black Fw200, olorBlack Fw2, ColorBlack Fw2V, ColorBlack Fw1, ColorBlack Fw18, ColorBlack S170, ColorBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, mention may be made of PrintexU, PrintexV, Printex140U, the Printex140V like.

  The carbon black in the present invention preferably has insulating properties. The carbon black having an insulating property is a carbon black exhibiting an insulating property when the volume resistance as a powder is measured by the following method. For example, an organic substance is adsorbed, coated, or coated on the surface of the carbon black particles. It means having an organic compound on the surface of carbon black particles, such as chemically bonded (grafted).

A coating solution is prepared by dispersing carbon black in propylene glycol monomethyl ether so that benzyl methacrylate and methacrylic acid have a molar ratio of 70:30 copolymer (mass average molecular weight 30,000) and 20:80 mass ratio. Then, after coating on a chromium substrate having a thickness of 1.1 mm and 10 cm × 10 cm to prepare a coating film having a dry film thickness of 3 μm, and further heating the coating film in a hot plate at 220 ° C. for about 5 minutes, A volume resistivity value is measured under an environment of 23 ° C. and a relative humidity of 65% by applying with a high resistivity meter manufactured by Mitsubishi Chemical Corporation, conforming to JIS K 6911, and Hirestar UP (MCP-HT450). Carbon black having a volume resistance value of 10 ⁵ Ω · cm or more, more preferably 10 ⁶ Ω · cm or more, and particularly preferably 10 ⁷ Ω · cm or more is preferable.

  Examples of carbon black include, for example, JP-A-11-60988, JP-A-11-60989, JP-A-10-330634, JP-A-11-80583, and JP-A-11-80584. The resin-coated carbon black described in Kaihei 9-124969 and JP-A-9-95625 can also be used.

  Examples of the titanium black suitable for the present invention include 12S, 13M, 13M-C, 13R-N, Ako Kasei Co., Ltd., and Tilac D manufactured by Mitsubishi Chemical Corporation.

  In addition, it is preferable that the photopolymerizable composition of this invention containing the above black coloring agents is used in order to form black films, such as a black matrix. Since this black film has a light shielding property and an antireflection property, it can be applied to the production of an antireflection film, a light shielding film and the like in addition to the black matrix.

In the photopolymerizable composition (1), when the colorant is a dye, a colored composition in a state of being uniformly dissolved in the composition can be obtained.
The dye that can be used as the colorant contained in the photopolymerizable composition (1) is not particularly limited, and conventionally known dyes for color filters can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be suitably used from the viewpoint of completely removing the binder and / or dye in the light non-irradiated part by development.
In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.

The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, and other components in the composition. It is selected in consideration of all required performance such as interaction with components, light resistance, heat resistance and the like.
Specific examples of the acid dye are shown below, but are not limited thereto. For example,
acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 45, 62, 70, 74, 80, 83, 86 , 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chroma violet K; acid Fuchsin; acid green 1, 3, 5 , 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18 , 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 0, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216 217,249,252,257,260,266,274; acid violet 6B, 7,9,17,19; acid yellow 1,3,7,9,11,17,23,25,29,34,36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; Food Yellow 3; and derivatives of these dyes.

Among these, acid black 24; acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1; acid orange 8, 51, 56, 63 , 74; acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217; acid violet 7; acid yellow 17, 25, 29, 34 , 42, 72, 76, 99, 111, 112, 114, 116, 184, 243; acidgreen 25 and the like and derivatives of these dyes are preferred.
Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Solvent orange 45; Rhodamine B, Rhodamine 110 and other acid dyes and derivatives of these dyes are also preferably used.

  Among these, as the colorant, triarylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazole azo It is preferable that the colorant is selected from a series, an anilinoazo series, a pyrazolotriazole azo series, a pyridone azo series, and an anthrapyridone series.

The colorant that can be used in the photopolymerizable composition (1) is a dye or an average particle size r (unit: nm) of 20 ≦ r ≦ 300, preferably 125 ≦ r ≦ 250, particularly preferably 30 ≦ r. A pigment satisfying ≦ 200 is desirable. By using a pigment having such an average particle diameter r, red and green pixels having a high contrast ratio and a high light transmittance can be obtained. Here, the “average particle size” means the average particle size of secondary particles in which primary particles (single crystallites) of the pigment are aggregated.
The particle size distribution of the secondary particles of the pigment that can be used in the present invention (hereinafter, simply referred to as “particle size distribution”) is 70% by mass of secondary particles having an average particle size of ± 100 nm. As mentioned above, it is desirable that it is 80 mass% or more.

  The pigment having the above average particle size and particle size distribution is preferably a commercially available pigment mixed with other pigments to be used (the average particle size usually exceeds 300 nm), preferably with a dispersant and a solvent. The pigment mixture can be prepared by mixing and dispersing while pulverizing using a pulverizer such as a bead mill or a roll mill. The pigment thus obtained is usually in the form of a pigment dispersion.

As content of the coloring agent contained in a photopolymerizable composition (1), it is preferable that it is 30-95 mass% in the total solid of a photopolymerizable composition, and 40-90 mass% is more preferable. 50-80 mass% is still more preferable.
If the amount of the colorant is too small, there is a tendency that an appropriate chromaticity cannot be obtained when a color filter is produced from the photopolymerizable composition (1). On the other hand, if the amount is too large, the photocuring does not proceed sufficiently and the strength as a film is lowered, or the development latitude at the time of alkali development tends to be narrow, but the (A) novel oxime compound used in the present invention is Since the light absorption efficiency is high, even when the colorant is contained in the photopolymerizable composition at a high concentration, the sensitivity improvement effect is remarkably exhibited.

[(1)-(D) Pigment dispersant]
When the photopolymerizable composition (1) contains a pigment as the colorant (C), it is preferable to add (D) a pigment dispersant from the viewpoint of improving the dispersibility of the pigment.

Examples of pigment dispersants that can be used in the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth) acrylates. , (Meth) acrylic copolymers, naphthalenesulfonic acid formalin condensates], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the pigment surface can be cited as preferred structures.
On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

Specific examples of the pigment dispersant that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, manufactured by EFKA, 4165 (polyurethane series), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (Azo face) Fee derivatives) ", Ajinomoto file Lee Ntekuno Co." AJISPER PB821, PB822 "manufactured by Kyoeisha Chemical Co., Ltd." Flowlen TG-710 (urethane oligomer) "," Polyflow No.50E, No.300 (acrylic copolymer) " “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725”, Kao, manufactured by Enomoto Kasei Co., Ltd. “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)”, “Acetami 86 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemical Co., Ltd., and the like.

  These dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.

As content of the dispersing agent in a photopolymerizable composition (1), it is preferable that it is 1-80 mass% with respect to a pigment, 5-70 mass% is more preferable, 10-60 mass% is still more preferable. .
Specifically, if a polymer dispersant is used, the amount of use thereof is preferably in the range of 5 to 100% by mass, more preferably in the range of 10 to 80% by mass with respect to the pigment.
In the case of using a pigment derivative, the amount used is preferably in the range of 1 to 30% by mass, more preferably in the range of 3 to 20% by mass, based on the pigment, A range of 15% by mass is particularly preferable.

  In the photopolymerizable composition (1), when using a pigment and a dispersant as the colorant, the total content of the colorant and the dispersant is determined from the viewpoint of curing sensitivity and color density. It is preferably 30% by mass or more and 90% by mass or less, more preferably 40% by mass or more and 85% by mass or less, and further preferably 50% by mass or more and 80% by mass or less with respect to the total solid content. preferable.

The photopolymerizable composition (1) may further contain optional components described in detail below, if necessary.
Hereinafter, optional components that can be contained in the photopolymerizable composition (1) will be described.

[(1)-(E) sensitizer]
The photopolymerizable composition (1) may contain a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and increasing the photosensitive wavelength.
As the sensitizer that can be used in the present invention, those that sensitize the above-mentioned (A) novel oxime compound by an electron transfer mechanism or an energy transfer mechanism are preferable.

Examples of the sensitizer used in the photopolymerizable composition (1) include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
That is, for example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), Thioxanthones (isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, Toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squaryu (Eg, squalium), acridine orange, coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes Carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, etc. Examples include aromatic ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.

  More preferable examples of the sensitizer in the photopolymerizable composition (1) include compounds represented by the following general formulas (e-1) to (e-4).

(In the general formula (e-1), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ¹ represents a base of the dye in combination with the adjacent A ¹ and carbon atom. R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. (W may represent an oxygen atom or a sulfur atom.)

(In the general formula (e-2), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ² —, where L ² is —O— or —S. In addition, W represents the same meaning as that shown in Formula (e-1).

(In the above general formula (e-3), A ² represents a sulfur atom or NR ⁵⁹ , and L ³ represents a non-metallic atomic group that forms a basic nucleus of the dye in combination with adjacent A ² and a carbon atom. , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represents a group of a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.)

(In the general formula (e-4), A ³ and A ⁴ each independently represents a sulfur atom or NR ⁶² , R ⁶² represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, L ⁴ and L ⁵ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in cooperation with adjacent A ³ , A ⁴ and a carbon atom, and R ⁶⁰ and R ⁶¹ each independently represent a monovalent group. It represents a non-metallic atomic group or can be bonded to each other to form an aliphatic or aromatic ring.)

The content of the sensitizer in the photopolymerizable composition (1) is preferably 0.1 to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency to the deep part and initiation decomposition efficiency. 0.5-15 mass% is more preferable.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

Moreover, as a preferable sensitizer which can be contained in the photopolymerizable composition (1), in addition to the above sensitizer, a compound represented by the following general formula (II) and a general formula (III) described later are used. And at least one selected from the following compounds.
These may be used individually by 1 type, and may use 2 or more types together.

In the general formula (II), R ¹¹ and R ¹² each independently represents a monovalent substituent, and R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. Represents a group. n represents an integer of 0 to 5, n ′ represents an integer of 0 to 5, and n and n ′ are not both 0. When n is 2 or more, a plurality of R ¹¹ may be the same or different. When n ′ is 2 or more, a plurality of R ¹² may be the same or different. In the general formula (II), the isomer by the double bond is not limited to either.

The compound represented by the general formula (II) preferably has a molar extinction coefficient ε at a wavelength of 365 nm of 500 mol ⁻¹ · L · cm ⁻¹ or more, and ε at a wavelength of 365 nm of 3000 mol ⁻¹ · L · cm ^{−. 1} or more is more preferable, and ε at a wavelength of 365 nm is most preferably 20000 mol ⁻¹ · L · cm ⁻¹ or more. It is preferable that the value of the molar extinction coefficient ε at each wavelength is in the above range because the sensitivity improvement effect is high from the viewpoint of light absorption efficiency.

Although the preferable specific example of a compound represented by general formula (II) is illustrated below, this invention is not limited to these.
Note that in this specification, a chemical formula may be described by a simplified structural formula, and a solid line or the like that does not clearly indicate an element or a substituent particularly represents a hydrocarbon group. In the following specific examples, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, n-Bu represents an n-butyl group, and Ph represents a phenyl group.

In the general formula (III), A represents an aromatic ring or a hetero ring which may have a substituent, X ² represents an oxygen atom, a sulfur atom, or —N (R ²³ ) —, and Y represents oxygen. It represents an atom, a sulfur atom, or = N (R ²³ ). R ²¹ , R ²² , and R ²³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A, R ²¹ , R ²² , and R ²³ are bonded to each other to form an aliphatic group Or you may form an aromatic ring.

In the general formula (III), R ²¹ , R ²² , and R ²³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group. When R ²¹ , R ²² , and R ²³ represent a monovalent nonmetallic atomic group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted group An aromatic heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, and a halogen atom are preferable.

In the compound represented by the general formula (III), Y is preferably an oxygen atom or ═N (R ²³ ) from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator. R ²³ represents a hydrogen atom or a monovalent nonmetallic atomic group. Furthermore, Y is most preferably ═N (R ²³ ).

  Hereinafter, preferred specific examples (VI1) to (VI124) of the compound represented by the general formula (III) are shown, but the present invention is not limited thereto. Further, it is not clear about an isomer by a double bond connecting an acidic nucleus and a basic nucleus, and the present invention is not limited to either isomer.

[(1)-(F) co-sensitizer]
The photopolymerizable composition (1) preferably further contains (F) a co-sensitizer.
In the present invention, the co-sensitizer further improves the sensitivity of (A) the novel oxime compound or (E) the sensitizer to active radiation, or suppresses the inhibition of polymerization of the polymerizable compound (B) by oxygen, etc. Has an effect.

  Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The content of these co-sensitizers is 0.1 to 30 mass with respect to the mass of the total solid content of the photopolymerizable composition (1) from the viewpoint of improving the curing rate due to the balance between the polymerization growth rate and chain transfer. % Is preferable, a range of 1 to 25% by mass is more preferable, and a range of 1.5 to 20% by mass is further preferable.

Moreover, it is preferable that a photopolymerizable composition (1) contains a thiol compound as a co-sensitizer.
As the thiol compound that can be contained in the photopolymerizable composition (1), a compound represented by the following general formula (IV) is preferable.

In the general formula (IV), X represents a sulfur atom, an oxygen atom, or —N (R ⁴³ ) —, and R ⁴³ represents a hydrogen atom having 1 to 5 carbon atoms or a C 6 to 13 carbon atom. Represents an aryl group. R ⁴¹ and R ⁴² are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a phenyl group optionally substituted with an alkoxy group having 1 to 8 carbon atoms. , A nitro group, an alkoxycarbonyl group having an alkyl group having 1 to 8 carbon atoms, a phenoxycarbonyl group, an acetyl group, or a carboxyl group, and R ⁴¹ , R ⁴² and a double bond to which these are bonded May form a benzene ring, and the double bond to which R ⁴¹ and R ⁴² are bonded may be hydrogenated.

  Moreover, as a thiol compound, the compound as described in the thiol compound of Unexamined-Japanese-Patent No. 53-702, Japanese Patent Publication No.55-500806, and Unexamined-Japanese-Patent No. 5-142772 is mentioned, for example.

  Furthermore, it is preferable that the thiol compound suitable for the photopolymerizable composition (1) is represented by the following general formula (V).

  In the general formula (V), R represents an alkyl group or an aryl group, and A represents an atomic group that forms a heterocycle together with N = CN.

In general formula (V), R represents an alkyl group or an aryl group.
Examples of the alkyl group include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms, linear groups having 1 to 12 carbon atoms, and 3 to 12 carbon atoms. More preferred are branched alkyl groups and cyclic alkyl groups having 5 to 10 carbon atoms.
Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group. , Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group , 2-norbornyl group and the like.

  Examples of the aryl group include a monocyclic structure, one to three benzene rings forming a condensed ring, and a benzene ring and a five-membered unsaturated ring forming a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, and the like. Among these, a phenyl group and a naphthyl group are more preferable.

  These alkyl groups and aryl groups may further have a substituent. Examples of the substituent that can be introduced include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, and the number of carbon atoms. A linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, and 2 carbon atoms -20 alkoxycarbonyloxy group, aryloxycarbonyloxy group having 7-20 carbon atoms, carbamoyloxy group having 1-20 carbon atoms, carbonamido group having 1-20 carbon atoms, 1-20 carbon atoms Sulfonamide group, carbamoyl group having 1 to 20 carbon atoms, sulfamoyl group, substituted sulfamoyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, carbon atom An aryloxy group having 6 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an N-acylsulfamoyl group having 1 to 20 carbon atoms, and 1 carbon atom -20 N-sulfamoylcarbamoyl group, C1-C20 alkylsulfonyl group, C6-C20 arylsulfonyl group, C2-C20 alkoxycarbonylamino group, C7-20 Aryloxycarbonylamino group, amino group, substituted amino group having 1 to 20 carbon atoms, imino group having 1 to 20 carbon atoms, ammonio group having 3 to 20 carbon atoms, carboxyl group, sulfo group, oxy group, Mercapto group, alkylsulfinyl group having 1 to 20 carbon atoms, arylsulfinyl group having 6 to 20 carbon atoms, and 1-2 carbon atoms Alkylthio group, arylthio group having 6 to 20 carbon atoms, ureido group having 1 to 20 carbon atoms, heterocyclic group having 2 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, sulfamoylamino group A substituted sulfamoylamino group having 1 to 2 carbon atoms, a silyl group having 2 to 20 carbon atoms, an isocyanate group, an isocyanide group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, A nitro group, an onium group, etc. are mentioned.

Moreover, in General formula (V), A represents the atomic group which forms a heterocyclic ring with N = CN.
Examples of atoms constituting this atomic group include a carbon atom, a nitrogen atom, a hydrogen atom, a sulfur atom, and a selenium atom.
The heterocycle formed by A and N═C—N may further have a substituent. Examples of the substituent that can be introduced include substituents that can be introduced into the alkyl group and aryl group. The same thing is mentioned.

  Moreover, as a thiol compound suitable for photopolymerizable composition (1), what is represented by the following general formula (VI) or general formula (VII) is more preferable.

In general formula (VI), R ¹ represents an aryl group, and X represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an aryl group.

In general formula (VII), R ² represents an alkyl group or an aryl group, and X represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an aryl group.

  As a halogen atom in general formula (VI) and (VII), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable.

  As the alkoxy group in the general formulas (VI) and (VII), methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, dodecyloxy group, benzyloxy group, allyloxy group Phenethyloxy group, carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, ant Loxyethoxyethoxy group, phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, cumyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group Group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group and the like.

The alkyl group in general formula (VI) and (VII) is synonymous with the alkyl group represented by R of general formula (V), and its preferable range is also the same.
Moreover, the aryl group in General formula (VI) and (VII) is synonymous with the aryl group represented by R of General formula (V), The preferable range is also the same.

  Each group in the general formulas (VI) and (VII) may further have a substituent, and the substituent can be introduced into the alkyl group or aryl group represented by R in the general formula (V). These are the same as those listed as examples of the substituent.

In general formulas (VI) and (VII), X is more preferably a hydrogen atom from the viewpoint of PGMEA solubility.
In general formula (VI), R ¹ is most preferably a phenyl group from the viewpoints of sensitivity and PGMEA solubility.
In general formula (VII), R ² is more preferably a methyl group, an ethyl group, a phenyl group, or a benzyl group from the viewpoints of sensitivity and PGMEA solubility.

  Of the general formulas (VI) and (VII), the compound represented by the general formula (VII) is most preferable from the viewpoint of solubility of PGMEA.

Hereinafter, although the preferable specific example of the thiol compound which can be used for this invention is shown, this invention is not limited to these.
Note that in this specification, a chemical formula may be described by a simplified structural formula, and a solid line or the like that does not clearly indicate an element or a substituent particularly represents a hydrocarbon group. In the following specific examples, Me represents a methyl group.

  The solubility of these thiol compounds in the PGMEA solvent is preferably 20 g / L or more, more preferably 20 g / L to 50 g / L, and still more preferably 20 g / L or more, from the viewpoint of coating film uniformity. 40 g / L or less.

-Solubility measurement method-
In the present specification, the solubility of the thiol compound is defined as follows. The specific thiol compound that can be completely dissolved when the specific thiol compound is added to 5 mL of propylene glycol monomethyl ether acetate (PGMEA) solvent and stirred at 25 ° C. for 1 hour. The maximum amount was taken as solubility.

  These thiol compounds are described in J. Org. Appl. Chem. , 34, 2203-2207 (1961).

A thiol compound may be used individually by 1 type, or may use 2 or more types together.
When a thiol compound is used in combination, only two or more compounds represented by any one of the general formulas described above may be used in combination, or a compound represented by a different general formula may be used in combination (for example, the general formula There is an embodiment in which a compound selected from the compounds represented by (VI) and a compound selected from the compounds represented by the general formula (VII) are used in combination.

  When the photopolymerizable composition (1) contains a thiol compound, the content thereof is the mass of the total solid content of the photopolymerizable composition from the viewpoint of improving the curing rate due to the balance between the polymerization growth rate and chain transfer. On the other hand, the range of 0.5-30 mass% is preferable, the range of 1-25 mass% is more preferable, and the range of 3-20 mass% is still more preferable.

[(1)-(G) Binder polymer]
In the photopolymerizable composition (1), a binder polymer can be further used as necessary for the purpose of improving the film properties. It is preferable to use a linear organic polymer as the binder. As such a “linear organic polymer”, a known one can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. , JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, a resin obtained by homo- or copolymerization of a monomer having a carboxyl group, acid anhydride Resins in which acid anhydride units are hydrolyzed, half-esterified or half-amidated, or epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride, etc. It is done. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  When an alkali-soluble resin is used as a copolymer, a monomer other than the above-mentioned monomers can also be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (12).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters having an aliphatic hydroxyl group such as methacrylic acid esters.
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like can be mentioned.

  Among these, a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane binder polymers containing acid groups described in No. 271741 and Japanese Patent Application No. 10-116232, and urethane binder polymers having acid groups and double bonds in side chains as described in JP-A No. 2002-107918 Is excellent in strength, and is advantageous in terms of printing durability and suitability for low exposure.
In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Application Laid-Open No. 2001-318463, and the like is preferable because of its excellent balance of film strength and developability.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The weight average molecular weight of the binder polymer that can be used in the photopolymerizable composition (1) is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably It is 1,000 or more, More preferably, it is the range of 2,000-250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.
These binder polymers may be any of random polymers, block polymers, graft polymers and the like.

The binder polymer that can be used in the present invention can be synthesized by a conventionally known method. Examples of the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used when synthesizing the binder polymer that can be used in the photopolymerizable composition (1) include known compounds such as an azo initiator and a peroxide initiator.

[(1)-(H) polymerization inhibitor]
In the photopolymerizable composition (1), a small amount of a thermal polymerization inhibitor is added to prevent unnecessary thermal polymerization of the polymerizable compound (B) during the production or storage of the photopolymerizable composition. Is desirable.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

The addition amount of the thermal polymerization inhibitor is preferably about 0.01 to about 5% by mass with respect to the total solid content of the photopolymerizable composition (1).
If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and may be unevenly distributed on the surface of the coating film during the drying process after coating. . The amount of the higher fatty acid derivative added is preferably from about 0.5 to about 10% by weight of the total composition.

[(1)-(I) Adhesion improver]
In the photopolymerizable composition (1), an adhesion improver can be added in order to improve adhesion to a hard surface such as a support. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane is most preferable.

  0.5-30 mass% is preferable in the total solid of a photopolymerizable composition (1), and, as for the addition amount of an adhesion improving agent, 0.7-20 mass% is more preferable.

[(1)-(J) Diluent]
The photopolymerizable composition (1) may use various organic solvents as a diluent.
The organic solvent used here is acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like.
These solvents can be used alone or in combination. The concentration of the solid content with respect to the organic solvent is preferably 2 to 60% by mass.

[(1)-(K) Other additives]
Furthermore, in order to improve the physical properties of the cured film, a known additive such as an inorganic filler, a plasticizer, or a sensitizer may be added to the photopolymerizable composition (1).
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. , 10% by mass or less can be added with respect to the total mass of the polymerizable compound and the binder polymer.

As described above, since the photopolymerizable composition (1) contains the novel oxime compound (A), it is cured with high sensitivity, has good storage stability, and further suppresses coloring when heated with aging. can do. In addition, when the photopolymerizable composition (1) is applied to a hard material surface and cured, it exhibits high adhesion to the surface.
Such a photopolymerizable composition (1) contains (A) a novel oxime compound, (B) a polymerizable compound, and (C) a colorant, and a photopolymerizable composition for a color filter (the color of the present invention). It is preferably used as a photopolymerizable composition for filters.

-Photopolymerizable composition (2)-
[(2)-(A) Novel oxime compound]
The novel oxime compound contained in the photopolymerizable composition (2) can function as a polymerization initiator in the composition.
The content of the novel oxime compound in the photopolymerizable composition (2) is preferably 0.5 to 40% by mass, more preferably 1 to 35% by mass, and more preferably 1.5 to 30% with respect to the total solid content of the composition. More preferred is mass%.

Also in the photopolymerizable composition (2), other known polymerization initiators other than the novel oxime compound may be used in combination as long as the effects of the present invention are not impaired.
Examples of other polymerization initiators include (a) aromatic ketones, (b) aromatic onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, (F) Ketooxime ester compounds, (g) borate compounds, (h) azinium compounds, (i) metallocene compounds, (j) active ester compounds, (k) compounds having a carbon halogen bond, and the like. More specifically, for example, polymerization initiators described in paragraph numbers [0081] to [0139] of JP-A-2006-78749 can be mentioned.

[(2)-(B) polymerizable compound]
Examples of the polymerizable compound (B) contained in the photopolymerizable composition (2) include the addition polymerizable compounds described above in the photopolymerizable composition (1).

  For these addition-polymerizable compounds, details of how to use, such as what type of structure to use, whether to use alone or in combination, how much is added, etc., according to the performance design of the final photosensitive material, Can be set arbitrarily. For example, it is selected from the following viewpoints. From the viewpoint of photosensitive speed, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functionalities are preferable. Further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether type). A method of adjusting both photosensitivity and intensity by using the compound) is also effective. A compound having a large molecular weight or a compound having a high hydrophobicity is not preferable in terms of development speed and precipitation in a developing solution, although it is excellent in photosensitive speed and film strength.

  In addition, the selection and use method of the addition polymerization compound is also an important factor for the compatibility and dispersibility with other components in the photosensitive layer (for example, binder polymer, initiator, colorant, etc.). The compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesion of the support, overcoat layer and the like. Regarding the compounding ratio of the addition polymerizable compound in the photosensitive layer, a larger amount is more advantageous in terms of sensitivity, but if it is too much, an undesirable phase separation occurs or a problem in the production process due to the adhesiveness of the photosensitive layer. For example, problems such as transfer of photosensitive material components and manufacturing defects due to adhesion, and precipitation from a developer may occur.

From these viewpoints, the content of the addition polymerizable compound is preferably 5 to 80% by mass, more preferably 25 to 75% by mass with respect to the total solid content of the photopolymerizable composition (2).
These addition polymerizable compounds may be used alone or in combination of two or more. In addition, the use method of the addition polymerizable compound can be arbitrarily selected from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface adhesiveness, etc. Depending on the case, a layer configuration and coating method such as undercoating and overcoating can be performed.

[(2)-(C) Binder polymer]
The photopolymerizable composition (2) preferably contains a binder polymer. The binder polymer is contained from the viewpoint of improving the film property, and various types can be used as long as it has a function of improving the film property.

  As the binder polymer, it is preferable to contain a linear organic polymer. Such “linear organic polymer” is not particularly limited, and any of them may be used. Preferably, a linear organic high molecular weight polymer that is soluble or swellable in water or weak alkaline water and that enables water development or weak alkaline water development is selected. The linear organic polymer is selected and used not only as a film-forming agent for the photopolymerizable composition but also according to the specifications of water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development is possible. Examples of such linear organic high molecular polymers include addition polymers having a carboxylic acid group in the side chain, such as JP 59-44615, JP-B 54-34327, JP-B 58-12777, and JP-B. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, methacrylic acid copolymer, acrylic acid copolymer , Itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, and the like. Similarly, an acidic cellulose derivative having a carboxylic acid group in the side chain may be mentioned. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful.

  Among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomers as required] copolymers, and [allyl (meth) acrylate / (meth) acrylic acid / necessary The other addition-polymerizable vinyl monomer] copolymer is suitable because it is excellent in the balance of film strength, sensitivity and developability.

  You may contain the binder polymer which has an amide bond or a urethane bond. Here, the binder polymer having an amide bond or a urethane bond is preferably a linear organic high molecular polymer having an amide bond or a urethane bond. Any of such “linear organic polymer having an amide bond or urethane bond” may be used. Preferably, a linear organic high molecular polymer having an amide bond or a urethane bond that is soluble or swellable in water or weak alkaline water that enables water development or weak alkaline water development is selected. The linear organic high molecular polymer having an amide bond or a urethane bond is selected and used not only as a film forming agent for the composition but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development is possible. As such a linear organic polymer having an amide bond or a urethane bond, for example, a binder having an amide group described in JP-A No. 11-171907 is suitable because it has both excellent developability and film strength.

  Also, Japanese Patent Publication No. 7-120040, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Publication No. 63-287944, Japanese Patent Publication No. 63-287947, Japanese Patent Publication No. Hei 1 The urethane-based binder polymer containing an acid group described in each of Japanese Patent No. 271741 and Japanese Patent Application No. 10-116232 is extremely excellent in strength, and is advantageous in terms of printing durability and low exposure suitability. is there. A binder having an amide group described in JP-A No. 11-171907 is suitable because it has excellent developability and film strength.

  In addition to these, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  The binder polymer can be mixed in the photopolymerizable composition (2) in any amount. From the standpoint of image intensity and the like, it is preferably in the range of 30 to 85% by mass with respect to the total solid content constituting the photosensitive layer. The addition polymerizable compound and the binder polymer are preferably in the range of 1/9 to 7/3 by mass ratio.

  In a preferred embodiment, a binder polymer that does not require water and is soluble in alkali is used. As a result, an organic solvent that is not environmentally preferable is not used as the developer, or the amount used can be limited to a very small amount. In such a method of use, the acid value of the binder polymer (the acid content per gram of the polymer expressed as a chemical equivalent number) and the molecular weight are appropriately selected from the viewpoint of image strength and developability. The preferred acid value is 0.4 to 3.0 meq / g, and the preferred molecular weight is in the range of 3000 to 500,000. More preferably, the acid value is in the range of 0.6 to 2.0 and the molecular weight is in the range of 10,000 to 300,000.

[(2)-(D) Sensitizer]
The photopolymerizable composition (2) preferably contains a sensitizer together with a polymerization initiator such as (A) a novel oxime compound. Examples of the sensitizer that can be used in the present invention include spectral sensitizing dyes, dyes or pigments that absorb light from a light source and interact with a polymerization initiator.

  Preferred spectral sensitizing dyes or dyes include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thianes). Carbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), phthalocyanines ( For example, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyll, chlorophyllin, central metal) Conversion chlorophyll), metal complexes (for example, the following compound), anthraquinones, such as (anthraquinone) squaryliums, include, for example, (squarylium), and the like.

  More preferable examples of spectral sensitizing dyes or dyes include those described in paragraph numbers [0144] to [0202] of JP-A-2006-78749, for example.

  Further, examples of the sensitizer applicable to the photopolymerizable composition (2) include those already described in the description of the photopolymerizable composition (1).

  A sensitizer may be used independently or may use 2 or more types together. The molar ratio of the total polymerization initiator to the sensitizing dye in the photopolymerizable composition (2) is 100: 0 to 1:99, more preferably 90:10 to 10:90, and most preferably 80: 20-20: 80.

[(2)-(E) Co-sensitizer]
To the photopolymerizable composition (2), a known compound having an action such as further improving sensitivity or suppressing polymerization inhibition by oxygen may be added as a co-sensitizer.

  Examples of the co-sensitizer include those already described in the explanation of the hard photopolymerizable composition (1). In addition to these, phosphorus compounds (such as diethyl phosphite) described in JP-A-6-250387, Si—H and Ge—H compounds described in Japanese Patent Application No. 6-191605, and the like are also included.

  When using a co-sensitizer, it is suitable to use 0.01-50 mass parts with respect to 1 mass part of total amounts of the polymerization initiator contained in a photopolymerizable composition (2).

[(2)-(F) polymerization inhibitor]
The photopolymerizable composition (2) contains a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the composition. It is desirable to add. As thermal polymerization inhibitors, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like can be mentioned.

  The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

[(2)-(G) Colorant, etc.]
Further, a dye or a pigment may be added for the purpose of coloring the photosensitive layer. Thereby, so-called plate inspection properties such as visibility after plate making and suitability for an image density measuring machine as a printing plate can be improved. As the colorant, many dyes cause a decrease in the sensitivity of the photopolymerization type photosensitive layer. Therefore, it is particularly preferable to use a pigment as the colorant. Specific examples include pigments such as phthalocyanine pigments, azo pigments, carbon black and titanium oxide, and dyes such as ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The addition amount of the dye and the pigment is preferably about 0.5% by mass to about 5% by mass of the total composition.

[(2)-(H) Other additives]
Furthermore, in order to improve the physical properties of the cured film, known additives such as inorganic fillers, other plasticizers, and a sensitizer capable of improving the ink inking property on the surface of the photosensitive layer may be added.

  Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of the compound which has an ionic unsaturated double bond, and a binder.

  Further, for the purpose of improving the film strength (printing durability), which will be described later, a UV initiator, a thermal crosslinking agent, or the like can be added to enhance the effect of heating and exposure after development.

<Color filter and manufacturing method thereof>
Next, the color filter of the present invention and the manufacturing method thereof will be described.
The color filter of the present invention is characterized by having a colored pattern formed on the support using the photopolymerizable composition for a color filter of the present invention.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

  The method for producing a color filter of the present invention comprises a step of applying a photopolymerizable composition for a color filter of the present invention on a support to form a colored photopolymerizable composition layer (hereinafter referred to as “colored photopolymerizable” as appropriate). Abbreviated as “composition layer forming step”), a step of exposing the colored photopolymerizable composition layer through a mask (hereinafter abbreviated as “exposure step” as appropriate), and the photopolymerization after exposure. And a step of developing the composition layer to form a colored pattern (hereinafter abbreviated as “development step” as appropriate).

Specifically, the photopolymerizable composition for a color filter of the present invention is applied on a support (substrate) directly or via another layer to form a photopolymerizable composition layer (colored photopolymerization). The composition layer forming step), exposing through a predetermined mask pattern, curing only the light-irradiated coating film portion (exposure step), and developing with a developer (developing step), each color (three colors) Alternatively, the color filter of the present invention can be manufactured by forming a patterned film composed of pixels of four colors).
Hereinafter, each process in the manufacturing method of the color filter of this invention is demonstrated.

[Colored photopolymerizable composition layer forming step]
In the colored photopolymerizable composition layer forming step, the colored photopolymerizable composition layer is formed by coating the photopolymerizable composition for a color filter of the present invention on a support.

As the support that can be used in this step, for example, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these glasses, imaging elements, etc. Examples of the photoelectric conversion element substrate include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  As a coating method of the photopolymerizable composition for a color filter of the present invention on a support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like are applied. be able to.

As a coating film thickness of the photopolymerizable composition for color filters, 0.1 μm to 10 μm is preferable, 0.2 μm to 5 μm is more preferable, and 0.2 μm to 3 μm is still more preferable.
Moreover, when manufacturing the color filter for solid-state image sensors, as a coating film thickness of the photopolymerizable composition for color filters, 0.35 micrometers-1.5 micrometers are preferable from a viewpoint of resolution and developability, 0 More preferably, it is 40 μm to 1.0 μm.

  The photopolymerizable composition for a color filter coated on the support is usually dried at 70 ° C. to 110 ° C. for about 2 minutes to 4 minutes to form a colored photopolymerizable composition layer.

[Exposure process]
In the exposure step, the colored photopolymerizable composition layer formed in the colored photopolymerizable composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferably used, and a high-pressure mercury lamp is more preferable. The irradiation intensity is more preferably ^5mJ / cm ^{2 ~1500mJ} / cm 2 is preferably ^{10mJ / cm 2 ~1000mJ / cm 2} , 10mJ / cm 2 ~800mJ / cm 2 being most preferred.

[Development process]
Subsequent to the exposure step, an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part remains.
As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

  Examples of the alkali used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0. ] -7- An alkaline aqueous solution obtained by diluting an organic alkaline compound such as undecene with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

  In the method for producing a color filter of the present invention, after the above-described photopolymerizable composition layer forming step, exposure step, and development step are performed, the formed colored pattern is heated and / or exposed as necessary. It may include a curing step for curing.

  By repeating the above-described colored photopolymerizable composition layer forming step, exposure step, and developing step (and, if necessary, the curing step) for the desired number of hues, a color filter having a desired hue is produced.

Here, as a method for producing the color filter of the present invention, the embodiment in which the photopolymerizable composition for a color filter of the present invention is used when forming the color pattern of the color filter has been mainly described. It is not limited. For example, the photopolymerizable composition for a color filter of the present invention can also be applied to the formation of a black matrix that isolates the colored pattern (pixels) constituting the color filter.
In addition, the colored photopolymerizable composition layer forming step, the exposure step, and the developing step (and, if necessary, the curing step) in the method for producing a color filter of the present invention are also applied when forming a black matrix on a substrate. The Specifically, using the photopolymerizable composition for a color filter of the present invention containing a black colorant such as carbon black and titanium black, as described above, a colored photopolymerizable composition layer forming step, an exposure step, Further, a black matrix (black pattern) can be formed on the substrate by performing a development process (and a curing process if necessary).

Since the color filter of the present invention uses the photopolymerizable composition for a color filter of the present invention, the formed colored pattern exhibits high adhesion to the support substrate, and the cured composition is resistant to development. Since it is excellent, it is possible to form a high-resolution pattern that has excellent exposure sensitivity, good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape. Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. That is, the color filter of the present invention is preferably applied to a solid-state image sensor.
The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

<Lithographic printing plate precursor>
Subsequently, the planographic printing plate precursor of the present invention will be described.
The lithographic printing plate precursor according to the invention has a photosensitive layer containing the photopolymerizable composition according to the invention on a support.
The lithographic printing plate precursor according to the invention may have other layers such as a protective layer and an intermediate layer as necessary. The lithographic printing plate precursor according to the invention contains a photopolymerizable composition according to the invention in the photosensitive layer, so that the sensitivity is high and the stability over time and the printing durability are excellent. Hereinafter, each element constituting the lithographic printing plate precursor according to the invention will be described.

(Photosensitive layer)
The photosensitive layer is a layer containing the photopolymerizable composition of the present invention. Specifically, the photopolymerizable composition (2), which is one of the preferred embodiments of the photopolymerizable composition of the present invention, is converted into a composition for forming a photosensitive layer (hereinafter referred to as “photosensitive layer composition” as appropriate). And a coating solution containing the composition can be coated on a support and dried to form a photosensitive layer.

  When the composition for photosensitive layer is applied on a support, each component contained in the composition is used by dissolving in various organic solvents. Solvents used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like. These solvents can be used alone or in combination. The solid content in the coating solution is suitably 2 to 50% by mass.

The coating amount of the support for the photosensitive layer mainly affects the sensitivity of the photosensitive layer, the developability, the strength of the exposed film, and the printing durability, and is preferably selected as appropriate according to the application. When the coating amount is too small, the printing durability is not sufficient. On the other hand, if the amount is too large, the sensitivity is lowered, it takes time for exposure, and a longer time is required for development processing, which is not preferable. As is the principal object lithographic printing plate for scan exposure of the present invention, the coating amount in the range in weight after drying of 0.1g ^/ m ² ~10g / m 2 are suitable. More preferably from ^{0.5g / m 2 ~5g / m 2} .

[Support]
As the support in the lithographic printing plate precursor according to the invention, a support having a hydrophilic surface is preferable. As the hydrophilic support, a conventionally known hydrophilic support used for a lithographic printing plate can be used without limitation.
The support is preferably a dimensionally stable plate, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.) ), Plastic films (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), metals as described above Includes laminated or vapor-deposited paper or plastic film, etc., and these surfaces are subjected to appropriate known physical and chemical treatments for the purpose of imparting hydrophilicity and improving the strength as necessary. Also good.

  In particular, preferable supports include paper, polyester film or aluminum plate, among which dimensional stability is good, relatively inexpensive, and a surface having excellent hydrophilicity and strength is provided by surface treatment as necessary. An aluminum plate which can be used is particularly preferred. A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferable.

  A suitable aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, and may also be a plastic film on which aluminum is laminated or vapor-deposited. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is at most 10% by mass. Particularly suitable aluminum in the present invention is pure aluminum, but completely pure aluminum is difficult to produce in the refining technique, and may contain slightly different elements. Thus, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate made of a publicly known material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, and particularly preferably 0.2 mm to 0.3 mm.

  In the case of a support having a surface of metal, particularly aluminum, roughening (graining) treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluoride zirconate, phosphate, or the like, or anodization treatment, etc. It is preferable that surface treatment is performed.

  The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening, a method of electrochemically dissolving and roughening a surface, and a method of selectively dissolving a surface chemically. This is done by the method of As the mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used. In addition, as an electrochemical surface roughening method, there is a method of performing alternating current or direct current in an electrolytic solution such as hydrochloric acid or nitric acid. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used. Further, prior to roughening the aluminum plate, for example, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution, or the like is performed in order to remove the rolling oil on the surface, if desired.

Furthermore, an aluminum plate that has been roughened and then immersed in an aqueous sodium silicate solution can be preferably used. As described in Japanese Examined Patent Publication No. 47-5125, an aluminum plate which has been anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. Anodizing treatment is carried out in an electrolytic solution in which an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid or boric acid, an organic acid such as oxalic acid or sulfamic acid, or an aqueous solution or a non-aqueous solution thereof, or a combination of two or more thereof. This is carried out by passing an electric current using the aluminum plate as an anode.

  Silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective.

  Furthermore, a support body provided with electrolytic grains as disclosed in JP-B-46-27481, JP-A-52-58602, and JP-A-52-30503, the above-mentioned anodizing treatment and sodium silicate A surface treatment combining treatments is also useful.

  Further, those obtained by sequentially performing mechanical surface roughening, chemical etching, electrolytic graining, anodizing treatment and sodium silicate treatment as disclosed in JP-A-56-28893 are also suitable.

  Furthermore, after performing these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having sulfonic acid groups in the side chain, polyacrylic acid, water-soluble metal salts (for example, zinc borate), or Those having a primer such as a yellow dye or an amine salt are also suitable.

  Further, a sol-gel treated substrate in which a functional group capable of causing an addition reaction by a radical as disclosed in JP-A-7-154983 is covalently used.

  Other preferred examples include those in which a water-resistant hydrophilic layer is provided as a surface layer on an arbitrary support. Examples of such a surface layer include a layer composed of an inorganic pigment and a binder described in US Pat. No. 3,055,295 and JP-A-56-13168, and a hydrophilic swelling described in JP-A-9-80744. Examples thereof include sol-gel films made of titanium oxide, polyvinyl alcohol, and silicic acids described in JP-A-8-507727.

  These hydrophilic treatments are performed to make the surface of the support hydrophilic, in order to prevent harmful reaction of the photopolymerizable composition provided thereon, and to improve the adhesion of the photosensitive layer. It is given for the purpose.

[Protective layer]
In the lithographic printing plate precursor according to the invention, it is preferable to further have a protective layer on the photosensitive layer. Protective layer prevents exposure to oxygen and low molecular weight compounds such as basic substances in the atmosphere that hinder the image formation reaction caused by exposure in the photosensitive layer, allowing exposure in the atmosphere And Therefore, the properties desired for such a protective layer are low permeability of low-molecular compounds such as oxygen, and further, transmission of light used for exposure is not substantially inhibited, and adhesion to the photosensitive layer is excellent. And it is desirable that it can be easily removed in the development process after exposure.

  Devices related to the protective layer have been conventionally used and are described in detail in US Pat. No. 3,458,311 and JP-A-55-49729. As a material that can be used for the protective layer, for example, a water-soluble polymer compound having relatively excellent crystallinity is preferably used. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, Water-soluble polymers such as polyacrylic acid are known. Of these, the use of polyvinyl alcohol as the main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability.

  The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether, and an acetal as long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components. Specific examples of polyvinyl alcohol include those having a hydrolysis rate of 71 to 100 mol% and a molecular weight in the range of 300 to 2400 in terms of mass average molecular weight. Specifically, Kuraray Co., Ltd. PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA- 420, PVA-613, L-8 and the like.

  Components of the protective layer (selection of PVA, use of additives), coating amount, and the like are selected in consideration of fogging, adhesion, and scratch resistance in addition to oxygen barrier properties and development removability. In general, the higher the hydrolysis rate of the PVA used (the higher the content of the unsubstituted vinyl alcohol unit in the protective layer), the higher the film thickness, the higher the oxygen barrier property and the more advantageous in terms of sensitivity. However, when the oxygen barrier property is extremely increased, there arises a problem that unnecessary polymerization reaction occurs during production and raw storage, and unnecessary fogging and image line thickening occur during image exposure. In addition, adhesion to the image area and scratch resistance are extremely important in handling the plate. Such a coating method for the protective layer is described in detail in, for example, US Pat. No. 3,458,311 and JP-A-55-49729.

  Furthermore, other functions can be imparted to the protective layer. For example, by adding a colorant (such as a water-soluble dye) that is excellent in the transmission of light from 350 nm to 450 nm and that can absorb light of 500 nm or more, which is used for exposure, it does not cause a decrease in sensitivity. Suitability can be further enhanced.

[Other layers]
In addition, it is possible to provide a layer for improving the adhesion between the photosensitive layer and the support and for improving the development removability of the unexposed photosensitive layer. For example, the addition of a compound having a relatively strong interaction with the substrate, such as a compound having a diazonium structure or a phosphone compound, or an undercoat layer can improve adhesion and increase printing durability. The addition of a hydrophilic polymer such as acrylic acid or polysulfonic acid or the undercoat layer improves the developability of the non-image area and improves the stain resistance.

[Plate making]
The lithographic printing plate precursor is usually subjected to image exposure, and then an unexposed portion of the photosensitive layer is removed with a developer to obtain an image.

  As the exposure method applicable to the lithographic printing plate precursor according to the invention, a known method can be used without limitation. The wavelength of the light source is desirably 350 nm to 450 nm, and specifically, an InGaN-based semiconductor laser is suitable. The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like. In addition, the photosensitive layer component can be made soluble in neutral water or weak alkaline water by using a highly water-soluble component, but a lithographic printing plate having such a configuration is loaded on a printing press. Thereafter, a system such as exposure-development can be performed on the machine.

  As an available laser light source of 350 to 450 nm, the following can be used.

As a gas laser, Ar ion laser (364 nm, 351 nm, 10 mW to 1 W), Kr ion laser (356 nm, 351 nm, 10 mW to 1 W), He—Cd laser (441 nm, 325 nm, 1 mW to 100 mW), and solid laser as Nd: Combination of YAG (YVO ₄ ) and SHG crystal × 2 times (355 nm, 5 mW to 1 W), combination of Cr: LiSAF and SHG crystal (430 nm, 10 mW), KNbO ₃ ring resonator (430 nm, 30 mW) as a semiconductor laser system A combination of a waveguide-type wavelength conversion element and AlGaAs, InGaAs semiconductor (380 nm to 450 nm, 5 mW to 100 mW), a combination of a waveguide-type wavelength conversion element, AlGaInP, and an AlGaAs semiconductor (300 nm to 350 nm, 5 mW to 00mW), AlGaInN (350nm~450nm, 5mW~30mW ), other, _{N 2} laser (337 nm as a pulse laser, pulse 0.1mJ~10mJ), XeF (351nm, pulse 10MJ～250mJ), and the like.

  Among these, an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 400 to 410 nm, 5 to 30 mW) is preferable in terms of wavelength characteristics and cost.

  Further, as a lithographic printing plate exposure apparatus of a scanning exposure method, there are an inner drum method, an outer drum method, and a flat bed method as an exposure mechanism, and all of the light sources other than the pulse laser can be used as a light source. it can. Practically, the following exposure apparatus is particularly preferable in terms of the relationship between the photosensitive material sensitivity and the plate making time.

・ Single beam exposure system that uses one gas laser or solid-state laser light source in the internal drum system ・ Multi-beam exposure system that uses many (10 or more) semiconductor lasers in the flat bed system ・ Many semiconductor lasers in the external drum system Multi-beam exposure equipment used (10 or more)

In the laser direct-drawing lithographic printing plate as described above, generally the photosensitive material sensitivity X (J / cm ² ), the photosensitive material exposure area S (cm ² ), the power q (W) of one laser light source, the laser Equation (eq1) is established between the number n and the total exposure time t (s).
X · S = n · q · t Formula (eq1)

i) In the case of the internal drum (single beam) system, the laser rotation speed f (radians / s), the sub-scanning length Lx (cm) of the photosensitive material, the resolution Z (dots / cm), and the total exposure time t (s) In general, equation (eq2) holds.
f · Z · t = Lx Formula (eq2)

ii) In the case of the external drum (multi-beam) system, the drum rotation speed F (radians / s), the photosensitive material sub-scanning length Lx (cm), the resolution Z (dots / cm), the total exposure time t (s), the number of beams In general, equation (eq3) is established during (n).
F · Z · n · t = Lx Formula (eq3)

iii) In the case of the flat bed (multi-beam) method, the rotational speed H (radian / s) of the polygon mirror, the sub-scanning length Lx (cm) of the photosensitive material, the resolution Z (dot / cm), the total exposure time t (s), Equation (eq4) is generally established between the number of beams (n).
H.Z.n.t = Lx Formula (eq4)

Resolution required for actual printing plate (2560 dpi), plate size (A1 / B1, sub-scan length 42 inch), exposure conditions of about 20 sheets / hour and photosensitive characteristics (photosensitive wavelength of the photopolymerizable composition of the present invention) By substituting (sensitivity: about 0.1 mJ / cm ² ) into the above formula, it can be understood that a combination with a semiconductor laser multi-beam exposure method is more preferable in the photosensitive material of the present invention. Further, by combining operability, cost, etc., a combination with an external drum type semiconductor laser multi-beam exposure apparatus is most preferable.

  Other exposure rays include ultra high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, visible and ultraviolet laser lamps, fluorescent lamps, tungsten lamps, solar Light or the like can also be used.

  Developers suitable for the lithographic printing plate precursor of the present invention include developers described in JP-B-57-7427, such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide. Inorganic alkaline agents and monoethanolamine, such as lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia Or an aqueous solution of an organic alkaline agent such as diethanolamine is suitable. It is added so that the concentration of such an alkaline solution is 0.1 to 10% by mass, preferably 0.5 to 5% by mass.

  Such an alkaline aqueous solution may contain a small amount of a surfactant, an organic solvent such as benzyl alcohol, 2-phenoxyethanol, and 2-butoxyethanol as necessary. Examples thereof include those described in US Pat. Nos. 3,375,171 and 3,615,480.

  Further, the developers described in JP-A-50-26601, 58-54341, JP-B-56-39464, and 56-42860 are also excellent.

A particularly preferred developer contains a nonionic compound represented by the following general formula (VIII) described in JP-A No. 2002-202616, has a pH of 11.5 to 12.8, and 3 Examples include a developer having a conductivity of ˜30 mS / cm.
A-W Formula (VIII)

In the general formula (VIII), A represents a hydrophobic organic group having a log P of AH of 1.5 or more, and W represents a nonionic hydrophilic organic group having a log P of W-H of less than 1.0. .
This developer component is described in detail in paragraphs (0024) to (0067) of JP-A No. 2002-202616.

  It is effective to add the nonionic compound represented by the general formula (VIII) to the developer in an amount of 0.1 to 15% by mass, preferably 1.0 to 8.0% by mass.

  In addition, in the plate making process of the lithographic printing plate precursor, the entire surface may be heated before exposure, during exposure, and between exposure and development, if necessary. By such heating, an image forming reaction in the photosensitive layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity may occur. Further, for the purpose of improving the image strength and printing durability, it is also effective to subject the developed image to full post heating or full exposure. Usually, heating before development is preferably performed under mild conditions of 150 ° C. or less. When it is 150 ° C. or lower, the problem of fogging does not occur in the non-image area. Very strong conditions are used for heating after development. Usually, it is the range of 200-500 degreeC. When the temperature is 200 ° C. or higher, sufficient image strengthening action can be obtained.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.

First, in Table 1 and Table 2 below , new oxime compounds (compound 1 to compound 6 ) , reference compounds (compound 7, compound 8), and comparative compounds (comparative compounds 1 to 1 ) used in Examples , Reference Examples and Comparative Examples are used. The detail of the comparison compound 4) is shown.

  Compounds 1 to 4 which are novel oxime compounds in Table 1 were synthesized by the method shown below.

(Synthesis Example 1: Synthesis of Compound 1 which is a novel oxime compound)
First, Compound A is synthesized according to the following scheme.
Ethylcarbazole (100.0 g, 0.512 mol) is dissolved in 260 ml of chlorobenzene, and after cooling to 0 ° C., aluminum chloride (70.3 g, 0.527 mol) is added. Subsequently, o-tolyl chloride (81.5 g, 0.527 mol) is added dropwise over 40 minutes, the temperature is raised to room temperature, and the mixture is stirred for 3 hours. Next, after cooling to 0 ° C., aluminum chloride (75.1 g, 0.563 mol) is added. 4-Chlorobutyryl chloride (79.4 g, 0.563 mol) is added dropwise over 40 minutes, and the mixture is warmed to room temperature and stirred for 3 hours. A mixed solution of 156 ml of 35 mass% hydrochloric acid aqueous solution and 392 ml of distilled water is cooled to 0 ° C., and the reaction solution is added dropwise. The precipitated solid was filtered with suction, washed with distilled water and methanol, and recrystallized with acetonitrile to obtain Compound A (yield 164.4 g, yield 77%) having the following structure.

Next, Compound B is synthesized using Compound A according to the following scheme.
Compound A (20.0 g, 47.9 mmol) is dissolved in 64 ml of THF and 4-chlorobenzenethiol (7.27 g, 50.2 mmol) and sodium iodide (0.7 g, 4.79 mmol) are added. Subsequently, sodium hydroxide (2.0 g, 50.2 mmol) is added to the reaction solution and refluxed for 2 hours. Next, after cooling to 0 ° C., SM-28 (11.1 g, 57.4 mmol) is added dropwise over 20 minutes, and the temperature is raised to room temperature and stirred for 2 hours. Next, after cooling to 0 ° C., isopentyl nitrite (6.73 g, 57.4 mmol) is added dropwise over 20 minutes, the temperature is raised to room temperature, and the mixture is stirred for 3 hours. The reaction solution is diluted with 120 ml of acetone and added dropwise to a 0.1N hydrochloric acid aqueous solution cooled to 0 ° C. The precipitated solid was filtered with suction and washed with distilled water. Subsequently, recrystallization was performed with acetonitrile to obtain Compound B having the following structure (yield: 17.0 g, yield: 64%).

Subsequently, compound 1 is synthesized by the following scheme using compound B.
Compound B (18.0 g, 32.4 mmol) was dissolved in 90 ml N-methylpyrrolidone and triethylamine (3.94 g, 38.9 mmol) was added. Next, after cooling to 0 ° C., acetyl chloride (3.05 g, 38.9 mmol) is added dropwise over 20 minutes, and then the temperature is raised to room temperature and stirred for 2 hours. The reaction solution was added dropwise to 150 ml of distilled water cooled to 0 ° C., and the precipitated solid was subjected to suction filtration, washed with 200 ml of isopropyl alcohol cooled to 0 ° C., dried, and then dried to give compound 1 having the following structure (yield 19.5 g, yield). 99%).

The structure of the obtained compound 1 was identified by NMR.
( ¹ H-NMR 400 MHz CDCl ₃ ): 8.86 (s, 1H), 8.60 (s, 1H), 8.31 (d, 1H, J = 8.0 Hz), 8.81 (d, 1H , J = 8.0 Hz), 7.51-7.24 (m.10H), 7.36 (q, 2H, 7.4 Hz), 3.24-3.13 (m, 4H), 2.36. (S, 3H), 2.21 (s, 3H), 1.50 (t, 3H, 7.4 Hz).

(Synthesis Example 2: Synthesis of Compound 2 as a Novel Oxime Compound)
Oxime compound C (17.6 g, 32.4 mmol) having the following structure was dissolved in 90 ml of N-methylpyrrolidone, and triethylamine (3.94 g, 38.9 mmol) was added. Next, after cooling to 0 ° C., acetyl chloride (3.05 g, 38.9 mmol) is added dropwise over 20 minutes, and then the temperature is raised to room temperature and stirred for 2 hours. The reaction solution was added dropwise to 150 ml of distilled water cooled to 0 ° C., and the precipitated solid was subjected to suction filtration, washed with 200 ml of isopropyl alcohol cooled to 0 ° C., dried, and then dried to give compound 2 having the following structure (yield 17.5 g, yield). 92%).

The structure of the obtained compound 2 was identified by NMR.
( ¹ H-NMR 400 MHz CDCl ₃ ): 8.89 (s, 1H), 8.65 (s, 1H), 8.32 (d, 1H, J = 8.8 Hz), 8.10 (d, 1H , J = 8.8 Hz), 7.86 (d, 1H, J = 7.0 Hz), 7.56-7.49 (m, 4H), 7.30-7.23 (m, 4H), 4 .46 (q, 2H, J = 7.2 Hz), 3.24-3.14 (m, 4H), 2.21 (s, 3H), 2.17 (s, 3H), 1.51 (t , 3H, J = 7.2Hz)

(Synthesis Example 3: Synthesis of Compound 3 which is a novel oxime compound)
Oxime compound D (17.3 g, 32.4 mmol) having the following structure was dissolved in 90 ml of N-methylpyrrolidone, and triethylamine (3.94 g, 38.9 mmol) was added. Next, after cooling to 0 ° C., acetyl chloride (3.05 g, 38.9 mmol) is added dropwise over 20 minutes, and then the temperature is raised to room temperature and stirred for 2 hours. The reaction solution was added dropwise to 150 ml of distilled water cooled to 0 ° C., and the precipitated solid was subjected to suction filtration, washed with 200 ml of isopropyl alcohol cooled to 0 ° C., dried, and then compound 3 having the following structure (yield 18.5 g, yield). 99%).

The structure of the obtained compound 3 was identified by NMR.
( ¹ H-NMR 400 MHz CDCl ₃ ): 8.86 (s, 1H), 8.59 (s, 1H), 8.33 (d, 1H, J = 8.4 Hz), 8.07 (d, 1H , J = 8.4 Hz), 7.50-7.26 (m, 8H), 7.11 (d, 2H, J = 9.2 Hz), 4.34 (q, 2H, J = 7.4 Hz) 3.19-3.14 (m, 4H), 2.37 (s, 3H), 2.31 (s, 3H), 2.18 (s, 3H), 1.49 (t, 3H, J = 7.4Hz)

(Synthesis Example 4: Synthesis of Compound 4 which is a Novel Oxime Compound)
Oxime compound E (17.7 g, 32.4 mmol) having the following structure was dissolved in 90 ml of N-methylpyrrolidone, and triethylamine (3.94 g, 38.9 mmol) was added. Next, after cooling to 0 ° C., acetyl chloride (3.05 g, 38.9 mmol) is added dropwise over 20 minutes, and then the temperature is raised to room temperature and stirred for 2 hours. The reaction solution was added dropwise to 150 ml of distilled water cooled to 0 ° C., and the precipitated solid was subjected to suction filtration, washed with 200 ml of isopropyl alcohol cooled to 0 ° C., dried, and then dried to give compound 4 (yield 17.5 g, yield). 92%).

The structure of the obtained compound 4 was identified by NMR.
( ¹ H-NMR 400 MHz CDCl ₃ ): 8.05 (d, 1H, J = 8.8 Hz), 7.78 (d, 1H, J = 8.8 Hz), 7.47 (d, 1H, J = 8.0 Hz), 7.42-7.26 (m, 10H), 3.19-3.08 (m, 4H), 2.35 (s, 3H), 2.17 (s, 3H)

In the same manner as in Synthesis Examples 1 to 4 , Compound 5 and Compound 6, which are novel oxime compounds described in Tables 1 and 2 , Compound 7 and Compound 8 which are reference compounds were synthesized.

  The structures of Comparative Compound 1 to Comparative Compound 3 shown in Table 2 are as follows.

[Example 1-1]
<Preparation and Evaluation of Photopolymerizable Composition 1>
Photopolymerizable composition 1 was prepared as follows and its sensitivity was evaluated.
0.08 mmol of the compound 1 as a novel oxime compound, 1 g of pentaerythritol tetraacrylate as a radical polymerizable compound, 1 g of polymethyl methacrylate (manufactured by Aldrich, molecular weight ca.996000) as a binder resin, and 16 g of cyclohexanone as a solvent A homogeneous composition containing was prepared. Using the obtained composition as a coating solution, this was coated on a glass plate with a spin coater and dried at 40 ° C. for 10 minutes to form a coating film having a thickness of 1.5 μm. A 21√2 step tablet (Dainippon Screen Mfg. Co., Ltd. gray scale film) is placed on this coating film, and the light from a 500 mW / cm ² high-pressure mercury lamp manufactured by USHIO ELECTRIC CO., LTD. The film was exposed for 30 seconds, and then impregnated in toluene for 60 seconds for development. When the number of steps completely cured and insolubilized corresponding to the step tablet was evaluated as sensitivity, the sensitivity was 9 steps.
In addition, a sensitivity step number shows that a sensitivity is so high that a number is large.

[Examples 1-2 to 1-6 , Reference Examples 1-7 and 1-8, Comparative Examples 1-1 to 1-4 ]
In Example 1-1, 0.08 mmol of the compound used as the novel oxime compound was added to each of the compounds shown in Table 1 and Table 2 (Compound 2 to Compound 8 and Comparative Compound 1 to Comparative Compound 4): 0. Photopolymerizable compositions 2 to 12 were prepared in exactly the same manner as in Example 1-1, except that each was replaced with 08 mmol, and the number of sensitivity steps was evaluated in the same manner as in Example 1-1.

The evaluation results of Examples 1-1 to 1-6 , Reference Examples 1-7 and 1-8, and Comparative Examples 1-1 to 1-4 are shown in Table 3 below.

[Example 2-1]
[1. Preparation of colored photopolymerizable composition A-1]
As a photopolymerizable composition for forming a color filter, a negative colored photopolymerizable composition A-1 containing a colorant (pigment) was prepared, and a color filter was produced using this.

1-1. Preparation of pigment dispersion (P1) C.I. I. Pigment Green 36 and C.I. I. 40 parts by mass of a 30/70 (mass ratio) mixture with CI Pigment Yellow 219, and 10 parts by mass (solid content conversion: about 4.4% by weight, BYK2001 (Disperbyk: manufactured by BYK), solid content concentration: 45.1% by mass). 51 parts by mass) and 150 parts by mass of ethyl 3-ethoxypropionate as a solvent were mixed and dispersed by a bead mill for 15 hours to prepare a pigment dispersion (P1).

  With respect to the obtained pigment dispersion (P1), the average particle diameter of the pigment was measured by a dynamic light scattering method and found to be 200 nm.

1-2. Preparation of colored photopolymerizable composition A-1 (coating liquid) The components of the following composition A-1 were mixed and dissolved to prepare a colored photopolymerizable composition A-1.

<Composition A-1>
Pigment dispersion (P1) 600 parts by mass Alkali-soluble resin 200 parts by mass (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, mol ratio: 80/10/10, Mw: 10,000)
Polyfunctional monomer dipentaerythritol hexaacrylate 60 parts by mass New oxime compound: 60 parts by mass of compound 1 Solvent: 1000 parts by mass of propylene glycol monomethyl ether acetate Surfactant (trade name: Tetranic 150R1, BASF ) 1 part by mass / γ-methacryloxypropyltriethoxysilane 5 parts by mass

[2. (Production of color filter)
2-1. Formation of the photopolymerizable composition layer The colored photopolymerizable composition A-1 containing the pigment obtained as described above was applied as a resist solution to a 550 mm × 650 mm glass substrate by slit coating under the following conditions, and then left for 10 minutes. While maintaining the state, vacuum drying and prebaking (100 ° C., 80 seconds) were performed to form a photopolymerizable composition coating film (photopolymerizable composition layer).

(Slit application conditions)
Gap at the opening at the tip of the coating head: 50 μm
Coating speed: 100 mm / second Clearance between substrate and coating head: 150 μm
Application thickness (dry thickness): 2 μm
Application temperature: 23 ° C

2-2. Exposure and Development Thereafter, the photopolymerizable composition layer was exposed in a pattern using a 2.5 kW ultra-high pressure mercury lamp. The entire surface of the photopolymerizable composition layer after exposure was covered with a 10% aqueous solution of an inorganic developer (trade name: CD, manufactured by FUJIFILM Electronics Materials Co., Ltd.) and allowed to stand for 60 seconds.

2-3. Heat treatment Thereafter, pure water was sprayed onto the photopolymerizable composition layer in a shower to wash away the developer, and then heated in an oven at 220 ° C. for 1 hour (post-bake). Thereby, a color filter having a colored pattern on the glass substrate was obtained.

[3. (Performance evaluation)
Storage stability and exposure sensitivity of a colored photopolymerizable composition, developability when a colored pattern is formed on a glass substrate using the colored photopolymerizable composition, coloring of the obtained colored pattern over time, substrate The adhesion and pattern cross-sectional shape were evaluated as follows. The evaluation results are summarized in Table 4.

3-1. Storage Stability of Colored Photopolymerizable Composition After storing the colored photopolymerizable composition at room temperature for 1 month, the degree of precipitation of foreign matters was visually evaluated according to the following criteria.
-Criteria-
○: No precipitation was observed.
Δ: Slight precipitation was observed.
X: Precipitation was recognized.

3-2. Exposure sensitivity of colored photopolymerizable composition The colored photopolymerizable composition was spin-coated on a glass substrate and then dried to form a coating film having a thickness of 1.0 µm. The spin coating conditions were 300 rpm for 5 seconds, 800 rpm for 20 seconds, and the drying conditions were 100 ° C. for 80 seconds. Next, the obtained coating film was 10 mJ / cm by a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having a super high pressure mercury lamp using a test photomask having a line width of 2.0 μm. It exposed with various exposure amount of ^{2 ~1600mJ} / cm ^2. Next, the exposed coating film was developed under the conditions of 25 ° C. and 60 seconds using a CDK-1 (Fuji Film Electronics Materials Co., Ltd.) developer diluted to 1%. Then, after rinsing with running water for 20 seconds, spray drying was performed to complete patterning.
Evaluation of exposure sensitivity evaluated the minimum exposure amount that the film thickness after the development of the area irradiated with light in the exposure process was 95% or more with respect to the film thickness 100% before exposure as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity.

3-3. Developability, pattern cross-sectional shape, substrate adhesion After developing the substrate surface and cross-sectional shape after post-baking in “2-3. Property, substrate adhesion, and pattern cross-sectional shape were evaluated. Details of the evaluation method are as follows.

<Developability>
In the exposure step, the presence or absence of residue in the area not irradiated with light (unexposed portion) was observed to evaluate developability. The evaluation criteria are as follows.
-Evaluation criteria-
○: Residue was not confirmed at all in the unexposed area. Δ: Residue was slightly confirmed at the unexposed area, but there was no practical problem. confirmed

<Coloring evaluation with forced heating over time>
The photopolymerizable composition layer (colored pattern) after the exposure and development was heated on a hot plate at 200 ° C. for 1 hour, and the color difference ΔEab ^* before and after heating was calculated based on the following criteria: MCPD- manufactured by Otsuka Electronics Co., Ltd. It was evaluated at 3000.
-Evaluation criteria-
○: ΔEab ^* ≦ 5
Δ: 5 <ΔEab ^* <8
×: ΔEab ^* ≧ 8

<Board adhesion>
The substrate adhesion was evaluated based on the following criteria by observing whether or not a pattern defect occurred.
-Evaluation criteria-
○: No pattern defects were observed Δ: Pattern defects were hardly observed, but partial defects were observed x: Remarkably many pattern defects were observed

<Pattern cross-sectional shape>
The cross-sectional shape of the formed pattern was observed and evaluated. The cross-sectional shape of the pattern is most preferably a forward taper, and a rectangular shape is next preferred. Reverse taper is not preferred. The results are shown in Table 4 below.

[Examples 2-2 to 2-6 , 2-9 to 2-15 , Reference Examples 2-7 and 2-8, Comparative Examples 2-1 to 2-4]
In composition A-1 used for the preparation of colored photopolymerizable composition A-1 in Example 2-1, 60 parts by mass of compound 1 (new oxime compound) was replaced with each compound and amount shown in Table 4 below. Examples 2-9 to 2-15 were all the same as Example 2-1 except that sensitizers and / or co-sensitizers were added in the types and amounts shown in Table 4 below. Colored photopolymerizable compositions A-2 to A-15 and A′-1 to A′-4 were prepared to obtain color filters. Furthermore, the same evaluation as in Example 2-1 was performed. The results are shown in Table 4.

  Sensitizers A1 to A3 and cosensitizers F1 to F3 shown in Table 4 are the compounds shown below.

From the results shown in Table 4, it can be seen that the colored photopolymerizable compositions of the Examples containing the novel oxime compounds (Compound 1 to Compound 6 ) are excellent in storage stability (time stability). In addition, these colored photopolymerizable compositions have high exposure sensitivity, developability when a colored pattern of a color filter is used for forming, and the resulting colored pattern is not colored with heating, and adheres to the substrate. It can also be seen that both the pattern cross-sectional shape is excellent.

[Example 3-1]
[1. Preparation of resist solution
Components of the following composition were mixed and dissolved to prepare a resist solution.
-Composition of resist solution-
-Propylene glycol monomethyl ether acetate (PGMEA) 19.20 parts by mass-Ethyl lactate 36.67 parts by mass-Resin 30.51 parts by mass [benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate copolymer (molar ratio) = 40/22/18) 40% PGMEA solution]
Dipentaerythritol hexaacrylate (polymerizable compound) 12.20 parts by mass Polymerization inhibitor (p-methoxyphenol) 0.0061 parts by mass Fluorosurfactant 0.83 parts by mass (F-475, Dainippon Ink (Chemical Industry Co., Ltd.)
-Photopolymerization initiator 0.586 parts by mass (TAZ-107 (trihalomethyltriazine photopolymerization initiator), manufactured by Midori Chemical Co., Ltd.)

[2. Fabrication of silicon wafer substrate with undercoat layer]
A 6 inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the resist solution is applied onto the silicon wafer so as to have a dry film thickness of 2 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer, thereby obtaining a silicon wafer substrate with an undercoat layer. It was.

[3. Preparation of colored photopolymerizable composition B-1]
The components of the following composition B-1 were mixed and dissolved to prepare a colored photopolymerizable composition B-1 containing a colorant (dye).

<Composition B-1>
-80 parts by mass of cyclohexanone-Colorant C.I. I. Acid Blue 108 7.5 parts by mass / colorant C.I. I. Solvent Yellow 162 2.5 parts by mass / radically polymerizable monomer (polymerizable compound) 7.0 parts by mass [3: 7 mixture of pentaerythritol triacrylate and dipentaerythritol hexaacrylate]
Compound 1 (new oxime compound) 2.5 parts by mass Glycerol propoxylate 0.5 parts by mass (number average molecular weight Mn: 1500, molar extinction coefficient ε = 0)

[4. Evaluation of Storage Stability of Colored Photopolymerizable Composition B-1 (Coating Liquid)]
After the colored photopolymerizable composition B-1 was stored at room temperature for 1 month, the degree of precipitation of foreign matters was visually evaluated according to the following criteria. The results are shown in Table 5 below.
-Criteria-
○: No precipitation was observed.
Δ: Slight precipitation was observed.
X: Precipitation was recognized.

[5. Production and Evaluation of Color Filter Using Colored Photopolymerizable Composition B-1]
3 above. The colored photopolymerizable composition B-1 prepared in 1. It was applied on the undercoat layer of the silicon wafer substrate with the undercoat layer obtained in (1) to form a photocurable coating film. Then, a heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.9 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), irradiation was performed at an exposure dose of 10 to 1600 mJ / cm ² through an Island pattern mask having a pattern of 2 μm square at a wavelength of 365 nm.
Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (FUJIFILM Corporation). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.

A silicon wafer substrate on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotational speed of 50 rpm by a rotating device, while being pure from above the rotation center. Water was supplied in a shower form from the ejection nozzle to perform rinsing, and then spray-dried.
As described above, a color filter having a colored pattern formed on the substrate was obtained.

<Exposure sensitivity and pattern size>
The minimum exposure amount in which the film thickness after development of the region irradiated with light in the exposure step was 95% or more with respect to 100% of the film thickness before exposure was evaluated as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity.
In addition, the size of the colored pattern was measured using a length measurement SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation). The closer the pattern size is to 2 μm, the better the curability and the better the sensitivity.
The results are shown in Table 5 below.

<Developability, coloring over time, substrate adhesion, pattern cross-sectional shape>
The evaluation of developability, coloring over time, substrate adhesion, and pattern cross-sectional shape was evaluated based on the evaluation method and evaluation criteria performed for Example 2-1. The results are shown in Table 5 below.

[Examples 3-2 to 3-6, 3-9, Reference Examples 3-7, 3-8, Comparative Examples 3-1 to 3-4]
In Example 3-1, 2.5 parts by mass of Compound 1 (new oxime compound) in Composition B-1 used for the preparation of colored photopolymerizable composition B-1 were each compound and amount shown in Table 5 below. Instead of Example 3-9, Example 3-9 was the same as Example 3-1, except that the sensitizers and co-sensitizers shown in Table 5 below were added in the types and amounts shown in Table 5 below. Colored photopolymerizable compositions B-2 to B-9 and B′-1 to B′-4 were prepared to obtain color filters. Furthermore, the same evaluation as in Example 3-1 was performed. The results are shown in Table 5.

  In addition, the sensitizer A3 and the co-sensitizer F3 shown in Table 5 are the compounds described above.

[Example 3-10]
The components of the following composition C-1 were mixed and dissolved to prepare a colored photopolymerizable composition C-1 containing a colorant (pigment).

<Composition C-1>
-Ethyl 3-ethoxypropionate [solvent] 17.9 parts by mass-Colorant C.I. I. Pigment Red 254 dispersion 26.7 parts by mass (solid content: 15% by mass, pigment content in the solid content: 60%)
-Colorant C.I. I. 17.8 parts by weight of Pigment Yellow 139 dispersion (solid content: 15% by mass, pigment content in the solid content: 60%)
Radical polymerizable monomer (polymerizable compound) 3.5 parts by mass [3: 7 mixture of pentaerythritol triacrylate and dipentaerythritol hexaacrylate]
Compound 1 (new oxime compound) 0.5 parts by mass Benzyl methacrylate / methacrylic acid copolymer 2.0 parts by mass (molar ratio = 70/30)

[Examples 3-11 to 3-15, 3-18 to 3-20, Reference Examples 3-16 and 3-17, Comparative Examples 3-5 to 3-8]
In Example 3-10, 0.5 part by mass of Compound 1 (new oxime compound) in Composition C-1 used for the preparation of colored photopolymerizable composition C-1 was added to each compound shown in Table 6 below and In place of the amount, Examples 3-18 to 3-20 were all carried out except that sensitizers and co-sensitizers shown in Table 6 below were added in the types and amounts shown in Table 6 below. In the same manner as in Example 3-10, colored photopolymerizable compositions C-2 to C-11 and C′-1 to C′-4 were prepared.

  Each colored photopolymerizable composition obtained was evaluated in the same manner as in Example 3-1. The results are shown in Table 6.

  In addition, sensitizers A1 and A3 and co-sensitizers F2 and F3 shown in Table 6 are the compounds described above.

[Example 3-21]
A compound of the following composition D-1 was mixed and dissolved to prepare a colored photopolymerizable composition D-1 containing a colorant (pigment).

<Composition D-1>
-Ethyl 3-ethoxypropionate [solvent] 17.9 parts by mass-Colorant C.I. I. Pigment Red 254 dispersion 33.34 parts by mass (solid content: 15% by mass, pigment content in the solid content: 60%)
-Colorant C.I. I. Pigment Yellow 139 dispersion 22.23 parts by mass (solid content: 15% by mass, pigment content in the solid content: 60%)
-Radical polymerizable monomer (polymerizable compound) 2.5 parts by mass [3: 7 mixture of pentaerythritol triacrylate and dipentaerythritol hexaacrylate]
Compound 1 (new oxime compound) 0.5 parts by mass Benzyl methacrylate / methacrylic acid copolymer 2.0 parts by mass (molar ratio = 70/30)

[Examples 3-22 to 3-2 6 , Reference Examples 3-27 and 3-28 , Comparative Examples 3-9 to 3-12]
In Example 3-21, 0.5 part by mass of compound 1 (new oxime compound) in composition D-1 used for preparation of colored photopolymerizable composition D-1 was added to each compound 0 shown in Table 7 below. Colored photopolymerizable compositions D-2 to C-8 and D′-1 to D′-4 were prepared in the same manner as Example 3-21 except that the amount was changed to 0.5 parts by mass.

  Each colored photopolymerizable composition obtained was evaluated in the same manner as in Example 3-1. The results are shown in Table 7.

From the results of Tables 5 to 7, it can be seen that the colored photopolymerizable compositions of the Examples containing the novel oxime compounds (Compounds 1 to 6 ) are excellent in storage stability (time-lapse stability). . In addition, these colored photopolymerizable compositions have high exposure sensitivity, developability when a colored pattern of a color filter is used for forming, and the resulting colored pattern is not colored with heating, and adheres to the substrate. It can also be seen that both the pattern cross-sectional shape is excellent.
Further, as is apparent from Table 7, even when the pigment content is large, it can be seen that the exposure sensitivity is excellent.

[Examples 4-1 to 4-7, Comparative examples 4-1 to 4-3]
<Production of support>
An aluminum plate made of material 1S having a thickness of 0.30 mm was used with a No. 8 nylon brush and an aqueous suspension of 800 mesh Pamiston, and its surface was grained and washed thoroughly with water. After etching by immersing in 10% sodium hydroxide at 70 ° C. for 60 seconds, washed with running water, neutralized with 20% HNO ₃ and washed with water. This aluminum plate was subjected to an electrolytic surface roughening treatment in a 1% nitric acid aqueous solution using a sinusoidal alternating current under a condition of VA = 12.7 V at an anode time electricity of 300 coulomb / dm ² . When the surface roughness was measured, it was 0.45 μm (Ra indication). Subsequently, the aluminum plate was immersed in a 30% H ₂ SO ₄ aqueous solution, desmutted at 55 ° C. for 2 minutes, and then placed on a grained surface in a 33 ° C., 20% H ₂ SO ₄ aqueous solution. Then, when anodized for 50 seconds at a current density of 5 A / dm ² , the thickness was 2.7 g / m ² .
As described above, a support for a lithographic printing plate precursor was obtained.

<Formation of photosensitive layer>
On the obtained support, a photosensitive layer coating solution having the following composition was applied so that the dry coating amount was 1.4 g / m ² and dried at 95 ° C. to form a photosensitive layer.

-Coating solution composition for photosensitive layer-
Addition polymerizable compound (compound described in Table 8 below) 0.80 parts by mass Binder polymer (compound described in Table 8 below) 0.90 parts by mass Sensitizer (compound described in Table 8 below) Addition None, or 0.10 parts by mass. Novel oxime compound or comparative compound (compound described in Table 8 below). 0.05 part by mass. Co-sensitizer (compound described in Table 8 below) No addition or 0.25 Part by mass / 0.02 part by mass of fluorosurfactant (Megafac F-177: manufactured by Dainippon Ink & Chemicals, Inc.)
-Thermal polymerization inhibitor 0.03 parts by mass (N-nitrosohydroxylamine aluminum salt)
-Ε-type copper phthalocyanine dispersion 0.2 parts by mass-Methyl ethyl ketone 16.0 parts by mass-Propylene glycol monomethyl ether 16.0 parts by mass

<Formation of protective layer>
On the obtained photosensitive layer, a 3% by weight aqueous solution of polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 550) was applied so that the dry coating weight was 2 g / m ² and dried at 100 ° C. for 2 minutes. Thus, a protective layer was formed.

  As described above, the lithographic printing plate precursors of the examples and the lithographic printing plate precursors of the comparative examples were obtained.

<Plate making>
The following exposure and development processes were performed on the lithographic printing plate precursor.

(exposure)
A lithographic printing plate precursor was obtained by using a violet LD (violet boxer manufactured by FFEI) with a wavelength of 405 nm, an exposure amount of 50 μJ / cm ² , a solid image and a dot image of 1 to 99% at 4,000 lines and 175 lines / inch. 1% increments) were scanned and exposed.

(developing)
Standard processing was carried out with an automatic developing machine (Fuji Film LP-850P2) charged with the following developer 1 and finishing gum solution “FP-2W” (Fuji Film Co., Ltd.). The preheating conditions were a plate surface temperature of 100 ° C., a developer temperature of 30 ° C., and an immersion time in the developer of about 15 seconds.

  Developer 1 had the following composition, pH was 11.5 at 25 ° C., and conductivity was 5 mS / cm.

-Composition of Developer 1-
・ Potassium hydroxide 0.15g
・ Polyoxyethylene phenyl ether (n = 13) 5.0g
・ Chillest 400 (chelating agent) 0.1g
・ Water 94.75g

[Evaluation]
The sensitivity and storage stability of the lithographic printing plate precursor were evaluated by the following methods. The results are shown in Table 8 together.

1. Evaluation of Sensitivity The lithographic printing plate precursor is exposed under the above conditions, and immediately after that, developed under the above conditions to form an image, and the area percentage of 50% halftone dots at that time is determined as a halftone dot area measuring device (Greta). Measured by G. Macbeth). The larger the number, the higher the sensitivity.

2. Image-part printing durability test As a printing machine, "R201" manufactured by Roland is used, and "GEOS-G (N)" manufactured by Dainippon Ink & Chemicals, Inc. is used as the ink. Printing was performed. The printed matter in the solid image portion was observed, and the printing durability was examined based on the number of sheets on which the image began to fade. The higher the number, the better the printing durability.

3. Evaluation of storage stability (forced change over time) All the same methods were used for sensitivity evaluation except that each lithographic printing plate precursor was sealed with aluminum kraft paper together with interleaving paper and allowed to stand at 60 ° C for 4 days. The halftone dot area was measured. Next, the difference between the halftone dot area with a standing at 60 ° C. for 4 days and the halftone dot area with no standing at 60 ° C. for 4 days was taken, and the change in halftone dot (Δ%) due to forced aging was measured. The smaller the absolute value of this number, the less the influence of forced aging, that is, the higher the aging stability.

As is apparent from Table 8 above, the planographic printing plate precursors of Examples 4-1 to 4-7 containing the novel oxime compound of the present invention in the photosensitive layer have high sensitivity, stability over time, and printing durability. It turns out that it is excellent.
On the other hand, the lithographic printing plate precursors of Comparative Examples 4-1 to 4-3 were inferior to the lithographic printing plate precursors of the examples in terms of high sensitivity, stability over time, and printing durability.

In Table 8, sensitizers A1 to A3 and cosensitizers F2 and F3 are the compounds described above. The comparative compound LD-5 is 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.
Further, the structures of the polymerizable compounds M, N, O and binder polymers B1, B2, B3 shown in Table 8 are shown below.

[Examples 5-1 to 5-4, 5-7 to 5-11, 5-14 to 5-16, 5-19 to 5-21, 5-24, Reference Examples 5-5 , 5-6, 5 -12, 5-13, 5-17, 5-18, 5-22, 5-23, Comparative Examples 5-1 to 5-16]
(Preparation of black photopolymerizable composition)
<Preparation of carbon black dispersion A>
The following composition 1 was subjected to a high viscosity dispersion treatment with two rolls to obtain a dispersion. The viscosity of the dispersion at this time was 70000 mPa · s.
Then, the following composition 2 was added to this dispersion, and it stirred for 3 hours using the homogenizer on 3000 rpm conditions. The obtained mixed solution was subjected to a fine dispersion treatment for 4 hours with a disperser using 0.3 mm zirconia beads (trade name: Dispermat manufactured by GETZMANN), and carbon black dispersion A (hereinafter referred to as CB dispersion A). Was written). At this time, the viscosity of the mixed solution was 37 mPa · s.

(Composition 1)
-Average primary particle size 15 nm carbon black (Pigment Black 7) 23 parts-Benzyl methacrylate / methacrylic acid copolymer propylene glycol monomethyl ether acetate 45% solution 22 parts (BzMA / MAA = 70/30 Mw: 30000)
・ Solsparth 5000 (manufactured by Zeneca) 1.2 parts

(Composition 2)
22 parts of a benzyl methacrylate / methacrylic acid copolymer propylene glycol monomethyl ether acetate 45% solution (BzMA / MAA = 70/30 Mw: 30000)
・ 200 parts of propylene glycol monomethyl ether acetate

<Preparation of Titanium Black Dispersion A>
The following composition 3 was subjected to a high viscosity dispersion treatment with two rolls to obtain a dispersion. The viscosity of the dispersion at this time was 40,000 mPa · s.
In addition, you may knead | mix for 30 minutes with a kneader before a high-viscosity dispersion process.

<Composition 3>
-Average primary particle size 75nm Titanium black 13M-C 39 parts (Mitsubishi Materials Corporation) (Pigment Black 35)
8 parts of propylene glycol monomethyl ether acetate solution of benzyl (meth) acrylate / (meth) acrylic acid copolymer (BzMA / MAA = 70/30, Mw: 30000, solid content 40% by mass)
・ 1 part of Solsperse 5000 (Zeneca)

The following component 4 was added to the obtained dispersion, and the mixture was stirred for 3 hours using a homogenizer at 3000 rpm. The obtained mixed solution was finely dispersed for 4 hours with a disperser (trade name: Dispermat GETZMANN Co., Ltd.) using 0.3 mm zirconia beads, and titanium black dispersion A (hereinafter referred to as TB dispersion). A.) was obtained.
At this time, the viscosity of the mixed solution was 7.0 mPa · s.

<Composition 4>
8 parts of propylene glycol monomethyl ether acetate solution of benzyl (meth) acrylate / (meth) acrylic acid copolymer (BzMA / MAA = 70/30 Mw: 30000, solid content 40% by mass)
・ 200 parts of propylene glycol monomethyl ether acetate

<Preparation of black photopolymerizable compositions E-1 to E-24 and E'-1 to E'-16>
Components of the following composition Ea were mixed with a stirrer to prepare black photopolymerizable compositions E-1 to E-14 and E′-1 to E′-8.

(Composition E-a)
-Methacrylate / acrylic acid copolymer (alkali-soluble resin) 1.6 parts by mass-Dipentaerythritol hexaacrylate 2.3 parts by mass-Ethoxylated pentaerythritol tetraacrylate 0.8 part by mass-CB described in Table 9 below Dispersion A or TB dispersion A 24 parts by mass, propylene glycol monomethyl ether acetate 10 parts by mass, ethyl-3-ethoxypropionate 8 parts by mass , novel oxime compound , reference compound or comparative compound described in Table 9 below
Amounts and co-sensitizers listed in Table 9 below: No addition of F3 or 0.1 parts by mass

  Components of the following composition E-b were mixed with a stirrer to prepare black photopolymerizable compositions E-15 to E-24 and E′-9 to E′-16.

(Composition Eb)
-Dipentaerythritol hexaacrylate 2.3 parts by mass-CB dispersion A or TB dispersion A shown in Table 10 below 24 parts by mass-Propylene glycol monomethyl ether acetate 10 parts by mass-Ethyl-3-ethoxypropionate 8 parts by mass -New oxime compounds , reference compounds, or comparative compounds described in Table 10 below
Amount and co-sensitizer described in Table 10 below: No addition of F3 or 0.1 parts by mass

[Evaluation]
The following evaluation was performed using the black photopolymerizable compositions E-1 to E-24 and E′-1 to E′-16 obtained as described above. The results are summarized in Table 9 and Table 10 below.

-Exposure sensitivity evaluation-
First, the exposure sensitivities of the black photopolymerizable compositions E-1 to E-24 and E′-1 to E′-16 obtained as described above were determined by the following methods and evaluated.

Using the black photopolymerizable compositions E-1 to E-24 and E′-1 to E′-16, the film thickness after coating with a hot plate at a surface temperature of 120 ° C. for 120 seconds after coating is 1.0 μm. The spin coating speed was adjusted so that the film was uniformly coated on a silicon wafer to obtain a 1.0 μm coating film.
Then, i-line stepper, using the FPA-3000iS + (manufactured by Canon Inc), through a mask having a pattern Aru drawn of 10nm of L & S (line and ^{space), 10mJ / cm 2 ~5100mJ /} cm 2 The exposure was performed at various exposure amounts.
After the irradiation, paddle development is performed for 60 seconds at 23 ° C. using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH), and then rinse is performed using pure water for 20 seconds in a spin shower. Washed with pure water. Thereafter, the adhering water droplets were removed with high-level air, and the substrate was naturally dried to obtain a black image pattern.
About each obtained colored image pattern, it evaluated on the following reference | standard using the optical microscope.

In the above exposure step, the film thickness after development in the region irradiated with light was measured to be the minimum exposure amount that was 95% or more with respect to the film thickness 100% before exposure, and this was evaluated as exposure sensitivity. .
A smaller exposure sensitivity value indicates higher sensitivity.

-Evaluation of storage stability (stability over time)-
Moreover, the following method evaluated the temporal stability (storage stability) of the black photopolymerizable compositions E-1 to E-24 and E'-1 to E'-16 obtained as described above. .
That is, after the black photopolymerizable compositions E-1 to E-24 and E′-1 to E′-16 were stored at room temperature for 1 month, the degree of precipitation of foreign matters was visually evaluated according to the following criteria.
-Criteria-
○: No precipitation was observed.
Δ: Slight precipitation was observed.
X: Precipitation was recognized.

-Developability evaluation-
Furthermore, the developability of the black photopolymerizable compositions E-1 to E-24 and E′-1 to E′-16 obtained as described above was evaluated by the following methods.
That is, in the exposure process in the above sensitivity evaluation, the presence or absence of a residue in an area not irradiated with light (unexposed portion) was observed to evaluate developability. The evaluation criteria are as follows.
-Evaluation criteria-
○: Residue was not confirmed at all in the unexposed area. Δ: Residue was slightly confirmed at the unexposed area, but there was no practical problem. confirmed

  As is apparent from Tables 9 and 10 above, it can be seen that the black photopolymerizable composition of each Example containing a novel oxime compound is excellent in storage stability (stability over time). In addition, these black photopolymerizable compositions have higher exposure sensitivity than the comparative examples, and are excellent in developability in unexposed areas, so that a good black pattern (colored pattern) is formed even with a small exposure amount. I understand that it is possible.

Claims (14)

The compound represented by the following general formula ( 2 ).

[In the general formula ( 2 ), R represents an acyl group, X represents an alkyl group , A represents an unsubstituted alkylene group, Y represents Y1 or Y2 below, Ar represents an unsubstituted phenyl group, It represents a phenyl group substituted with an alkyl group or a phenyl group substituted with a halogen . n is an integer of 0-2. ]
It is represented by the following general formula ( 3 ), The compound of Claim 1 characterized by the above-mentioned.

[In the above general formula ( 3 ), R represents an acyl group, X represents an alkyl group , A represents an unsubstituted alkylene group, Ar represents an unsubstituted phenyl group, a phenyl group substituted with an alkyl group, Alternatively, it represents a phenyl group substituted with halogen . n is an integer of 0-2. ] In the general formula (2) or (3), R is an acetyl group, X is a methyl group, Ar is an unsubstituted phenyl group, a phenyl group substituted with a methyl group, or Cl or Br. The compound according to claim 1, wherein the compound represents a phenyl group. In the general formula (2) or (3), A is —CH. ₂ CH ₂ The compound according to any one of claims 1 to 3, wherein the compound is-. 2. The compound according to claim 1, wherein the compound represented by the general formula (2) is any one of the following compounds 1 to 6.
(A) A photopolymerizable composition comprising the compound according to any one of claims 1 to 5 and (B) a polymerizable compound. The photopolymerizable composition according to claim 6 , further comprising (C) a colorant. The photopolymerizable composition according to claim 7 , wherein the colorant (C) is a pigment and further contains a pigment dispersant (D). The photopolymerizable composition according to claim 7 or 8 , wherein the (C) colorant is a black colorant. A photopolymerizable composition for a color filter, comprising the photopolymerizable composition according to any one of claims 7 to 9 . A color filter comprising a colored pattern formed using the photopolymerizable composition for a color filter according to claim 10 on a support. Applying a photopolymerizable composition for a color filter according to claim 10 on a support to form a photopolymerizable composition layer;
Exposing the photopolymerizable composition layer through a mask;
Developing the photopolymerizable composition layer after exposure to form a colored pattern; and
A method for producing a color filter, comprising: A solid-state imaging device comprising the color filter according to claim 11 . A lithographic printing plate precursor comprising a photosensitive layer containing the photopolymerizable composition according to claim 6 on a support.