JP5317879B2 - NOVEL COMPOUND, POLYMERIZABLE COMPOSITION, COLOR FILTER, COLOR FILTER MANUFACTURING METHOD, SOLID-STATE IMAGING ELEMENT, AND PLATE PRINTING PRINTING PLATE - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition having high sensitivity to light of 365 nm or 405 nm wavelength and allowing a cured film with excellent intra-film curability to be formed. <P>SOLUTION: The polymerizable composition comprises (A) an oxime-based polymerization initiator having a condensed ring structure formed from a monocyclic structure selected from aromatic rings and heteroaromatic rings and an aliphatic monocyclic structure containing an oxime group bonding directly to a carbonyl group, and (B) a polymerizable compound. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a polymerizable composition, a novel compound useful as a polymerization initiator in the polymerizable compound, a color filter using the polymerizable compound and a method for producing the same, a solid-state imaging device including the color filter, and the The present invention relates to a lithographic printing plate precursor provided with a photosensitive layer comprising a polymerizable composition.

  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 photoinitiator, there exists another aspect which generate | occur | produces an acid by irradiation of light and uses the generated acid as a catalyst, for example. Specifically, it is used as a material for image formation, anti-counterfeiting, detection of energy dose by utilizing the coloring reaction of a dye precursor catalyzed by the generated acid, or decomposition using the generated acid as a catalyst. It is used for positive resists for semiconductor manufacturing, TFT manufacturing, color filter manufacturing, micromachine component manufacturing, etc. using reaction.

  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, in general, a photopolymerization initiator excellent in sensitivity lacks stability, and thus a photopolymerization initiator that satisfies the improvement in sensitivity and storage stability is desired.

Then, an oxime ester derivative is proposed as a photoinitiator used for a photopolymerizable composition (for example, refer patent documents 1-6). However, since these known oxime ester compounds have low absorbance at a wavelength of 365 nm and a wavelength of 405 nm, there is still room for improvement with respect to the exposure sensitivity at this wavelength.
Moreover, the present condition is that the photopolymerizable composition is excellent in storage stability and has excellent sensitivity to light having a short wavelength such as 365 nm and 405 nm.

Such a polymerizable composition containing an oxime-based initiator is applied to various fields, and is used, for example, for forming a colored region of a color filter or a photosensitive layer of a lithographic printing plate precursor.
For example, a colored radiation-sensitive composition for a color filter containing an oxime compound as a polymerization initiator is disclosed (see, for example, Patent Document 7), but regarding storage stability and sensitivity to light of a short wavelength, It was still insufficient. In other words, the formation of a colored pattern having absorption in visible light often includes a large amount of a colorant having absorption in the visible region. Therefore, when the absorption wavelength and the exposure wavelength overlap, the exposure energy is changed to the composition layer. However, when the surface is hardened, the curability on the inner surface of the film is insufficient, and there is a concern about peeling in an undesired region at the time of development in the color filter, and when used for a lithographic printing plate precursor There is a concern that the printing durability will be reduced.
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 2006-342166 A JP 2007-231000 A JP-A-2005-202252

The first object of the present invention is to cure with high sensitivity to exposure, and to form a cured film having excellent film internal curability because of high transparency and high sensitivity to light with a wavelength of 365 nm or 405 nm. It is to provide a possible polymerizable composition.
The second object of the present invention is to form a colored pattern that is cured with high sensitivity, has good pattern formability and excellent adhesion to the support, and has excellent pattern shape even after post-heating after development. And a photopolymerizable composition used for forming a colored region of a color filter.
The third object of the present invention is to use a photopolymerizable composition used for forming a colored region of the color filter, having a good pattern shape and a colored pattern having excellent adhesion to a support. Another object of the present invention is to provide a color filter, a manufacturing method capable of manufacturing the color filter with high productivity, and a solid-state imaging device including the color filter.
A fourth object of the present invention is to provide a lithographic printing plate precursor capable of forming an image with high sensitivity using the photopolymerizable composition.
It is a further object of the present invention to provide a novel oxime compound that can be suitably used in the polymerizable composition.

As a result of intensive studies, the present inventors have shown that the use of an oxime compound having a specific structure has a good absorbance for the film internal curability with respect to light having a wavelength of 365 nm or 405 nm, and has a storage stability. In addition, the inventors have obtained knowledge that a photopolymerizable composition that is also excellent can be obtained. Further, it has been found that such a polymerizable composition also has an accompanying effect that coloring due to heating is suppressed.
In addition, this inventor discovered that what has a structure shown in following General formula (3) among this oxime compound is a novel compound.
Specific means for solving the above problems will be described below.

<1> (A) An oxime having a condensed ring structure formed from a monocyclic structure selected from an aromatic ring and a heteroaromatic ring, and an aliphatic monocyclic structure including an oxime group directly bonded to a carbonyl group A polymerizable composition comprising a system polymerization initiator and (B) a polymerizable compound.
<2> The polymerizable composition according to <1>, wherein the (A) oxime polymerization initiator is a compound represented by the following general formula (1).

In the general formula (1), Ar represents a monocyclic structure selected from an aromatic ring and a heteroaromatic ring. A represents a single bond or a divalent linking group. X represents —CH ₂ —, —O—, —S— or —NR—, and R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ^1A and R ^1B each independently represent a hydrogen atom, an alkyl group or an aryl group. R ³ represents an acyl group or a sulfonyl group.
<3> The polymerizable composition according to <1> or <2>, wherein the (A) oxime polymerization initiator is a compound represented by the following general formula (2).

In the general formula (2), A represents a single bond or an alkylene group having 1 to 2 carbon atoms. X represents —CH ₂ —, —O—, —S— or —NR—, and R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ^1A and R ^1B each independently represent a hydrogen atom, an alkyl group or an aryl group. R ³ represents an acyl group or a sulfonyl group.
R ² , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, hydroxyl group, alkoxy group, aryloxy group, amino group, mercapto group Represents an alkylthio group or an arylthio group.

<4> The polymerizable composition according to <1> or <2>, wherein the (A) oxime polymerization initiator is a compound represented by the following general formula (3).

In the general formula (3), R ^1A and R ^1B each independently represent a hydrogen atom, an alkyl group, or an aryl group. R ³ represents an acyl group or a sulfonyl group.
R ² , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, hydroxyl group, alkoxy group, aryloxy group, amino group, mercapto group Represents an alkylthio group or an arylthio group.
<5> The polymerizable composition according to any one of <1> to <4>, further comprising (C) a colorant.

<6> The polymerizable composition according to <5>, wherein the (C) colorant is a pigment and further contains (D) a pigment dispersant.
<7> The polymerizable composition according to <5> or <6>, wherein the (C) colorant is a black colorant.

<8> The polymerizable composition according to any one of <5> to <7>, which is used for forming a colored region of a color filter.
<9> A color filter having a colored region formed on the support using the polymerizable composition according to <8>.

<10> On the support, the step of applying the polymerizable composition according to <8> to form a polymerizable composition layer, the step of exposing the polymerizable composition layer in a pattern, and exposure Developing the later polymerizable composition layer to form a colored pattern;
A method for producing a color filter comprising:

<11> A solid-state imaging device including the color filter according to <9>.
<12> A lithographic printing plate precursor having a photosensitive layer containing the polymerizable composition according to any one of <1> to <5> on a support.

<13> A compound represented by the following general formula (3).

In the general formula (3), R ^1A and R ^1B each independently represent a hydrogen atom, an alkyl group, or an aryl group. R ³ represents an acyl group or a sulfonyl group.
R ² , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, hydroxyl group, alkoxy group, aryloxy group, amino group, mercapto group , An alkylthio group, or an arylthio group.

According to the present invention, it has high transparency to light with a wavelength of 365 nm or 405 nm and high sensitivity, so that it has excellent film internal curability, excellent storage stability, and further suppresses coloring due to heating over time. It is possible to provide a polymerizable composition capable of forming a cured film, and an oxime compound suitably used for the polymerizable composition.
Further, according to the present invention, it is excellent in storage stability, cured with high sensitivity, has a good pattern forming property, forms a colored pattern with excellent adhesion to a support, and is also suitable for post-heating after development. A polymerizable composition having an excellent pattern shape and used for forming a colored region of a color filter can be provided.
Furthermore, a color filter having a colored pattern having a good pattern shape and excellent adhesion to a support, comprising the polymerizable composition used for forming the colored region of the color filter, 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.
Furthermore, a lithographic printing plate precursor capable of forming an image with high sensitivity using the polymerizable composition can be provided.

  The polymerizable composition of the present invention is formed from (A) a monocyclic structure selected from an aromatic ring and a heteroaromatic ring, and an aliphatic heteromonocyclic structure comprising an oxime group directly bonded to a carbonyl group. And an oxime polymerization initiator having a condensed ring structure (hereinafter referred to as a specific oxime compound as appropriate) and (B) a polymerizable compound.

The (A) specific 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 specific oxime compound has excellent sensitivity to a light source of 365 nm or 405 nm, it exhibits an excellent effect when used as a photopolymerization initiator in a photopolymerizable composition.
Hereinafter, each component contained in the polymerizable compound of the present invention will be described.

<(A) An oxime system having a condensed ring structure formed from a monocyclic structure selected from an aromatic ring and a heteroaromatic ring, and an aliphatic heterocyclic monocyclic structure comprising an oxime group directly bonded to a carbonyl group Polymerization initiator>
The specific oxime compound in the present invention is formed from (a1) a monocyclic structure selected from an aromatic ring and a heteroaromatic ring, and (a2) an aliphatic monocyclic structure comprising an oxime group directly bonded to a carbonyl group. In other words, a monocyclic structure composed of an aromatic ring which may contain a heteroatom and a monocyclic structure formed including a partial structure having an oxime-initiating ability are fused. And a compound having a condensed ring structure formed from only two rings.

The (a1-1) aromatic ring constituting the condensed ring is preferably an aromatic ring having 5 to 30 carbon atoms, more preferably 5 to 15 carbon atoms, and still more preferably an aromatic ring having 5 or 6 carbon atoms. It is a ring.
Specific examples of the aromatic ring include benzene.
As the (a1-2) heteroaromatic ring, an aromatic monocyclic structure containing at least one hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom among atoms constituting the aromatic ring Point to.
(A1-2) The heteroaromatic ring is preferably a heteroaromatic ring containing a nitrogen atom, an oxygen atom or a sulfur atom, and more preferably a heteroaromatic ring containing a sulfur atom.

Specific examples of the heterocyclic ring include pyrrole, furan, thiophene, pyridine, pyrazine, pyrimidine, pyridazine, piperazine, pyran, chroman, imidazole, thiazole, pyrazole, morpholine, and the like, and pyrrole, furan, thiophene, Pyridine is preferable, furan, thiophene, and pyridine are more preferable, and thiophene and pyridine are more preferable.
The monocyclic structure selected from the (a1) aromatic ring and heteroaromatic ring in the present invention is composed of only one ring structure literally, and does not include a structure having two or more rings.

  The specific oxime compound of the present invention includes (a2) an oxime group that is bonded to the monocyclic structure by condensation in addition to the single aromatic ring or heterocyclic ring, that is, a fatty acid containing a partial structure having an oxime-based initiating ability. Group monocyclic structure. The ring structure having an oxime group is preferably an aliphatic hydrocarbon ring formed by condensation with the above-described single ring. Substitution of an oxime group on a condensed ring formed by a monocyclic structure selected from (a1) an aromatic ring and a heteroaromatic ring and (a2) an aliphatic monocyclic structure comprising an oxime group directly bonded to a carbonyl group The position is the α-position, β-position or γ-position of the adjacent (hetero) aromatic ring, preferably the α-position or β-position. This aliphatic monocyclic structure may contain heteroatoms such as a nitrogen atom, oxygen atom, sulfur atom, and phosphorus atom as atoms constituting the ring, and is an aliphatic heteromonocyclic structure containing a sulfur atom. Preferably there is.

  (A) The specific oxime compound includes (a1) a monocyclic structure selected from aromatic rings and heteroaromatic rings and (a2) an aliphatic heteromonocyclic structure comprising an oxime group directly bonded to a carbonyl group. Although it will not be restrict | limited especially if it is a compound which has the condensed ring structure formed, It is especially preferable that it is a compound represented by following General formula (1).

In the general formula (1), Ar represents a monocyclic structure selected from an aromatic ring and a heteroaromatic ring. A represents a single bond or a divalent linking group. X represents —CH ₂ —, —O—, —S— or —NR—, wherein R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ^1A and R ^1B each independently represent a hydrogen atom, an alkyl group or an aryl group. R ³ represents an acyl group or a sulfonyl group.

In the general formula (1), the monocyclic structure selected from the aromatic ring and the heteroaromatic ring represented by Ar has the same meaning as the above-described monocyclic ring, and the preferred range is also the same.
In the present specification, the aromatic ring, heteroaromatic ring, acyl group, sulfonyl group, alkyl group, and aryl group may further have a substituent unless otherwise specified.

  In general formula (1), A represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, and an amide group, and among them, an alkylene group and a carbonyl group are preferable.

In General Formula (1), when R ³ represents an acyl group, the acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. And more preferably an acyl group having 2 to 7 carbon atoms.
Specific examples include, for example, acetyl group, propanoyl group, butanoyl group, t-butyl group, 1-adamantyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, toluyl group, 1-naphthoyl group and 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 group, acrylic group, methacrylic group Group, etc. It is.

  Among the above specific examples, the acyl group is preferably an acetyl group, a propanoyl group, a benzoyl group, or a toluyl group, and more preferably an acetyl group or a benzoyl group.

When R ³ represents a sulfonyl group, examples of the sulfonyl group include an alkylsulfonyl group and an arylsulfonyl group which may have a substituent. Among them, an alkylsulfonyl group and an alkyl group in the alkylsulfonyl group A halogenated alkylsulfonyl group in which a part of the hydrogen atom is replaced by a halogen atom is preferred, and a fluoroalkylsulfonyl group in which a part of the hydrogen atom of the alkyl group is replaced by a fluorine atom is more preferred.
Specific examples include a nonafluorobutanesulfonyl group and a perfluorooctanesulfonyl group.

Among these, from the viewpoint of increasing sensitivity, R ³ in the general formula (1) is more preferably an acyl group, specifically, an acetyl group, an ethyloyl group, a propioyl group, a benzoyl group, or a toluyl group is preferable. .

In the general formula (1), X represents —CH ₂ —, —O—, —S— or —NR—, wherein R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and is highly sensitive. From the viewpoint of chemical conversion, —O—, —S— or —NR— is more preferable, and —S— or —O— is still more preferable. Most preferred is -S-.

In General Formula (1), R ^1A and R ^1B each independently represent a hydrogen atom, an alkyl group, or an aryl group. Preferably, R ^1A is a hydrogen atom, and R ^1B is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a phenyl group, a benzyl group, an allyl group, or a propargyl group, and more preferably R ^1A Is a hydrogen atom and R ^1B is a methyl group.

  Furthermore, the aromatic ring that may have a substituent, the heterocyclic ring that may have a substituent, and the acyl group that may have a substituent may be further substituted with another substituent. .

  Examples of the substituent that can be further introduced into each substituent in the general formula (1) include a halogen group such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, an alkoxy such as a methoxy group, an ethoxy group, and a tert-butoxy group. Groups, phenoxy groups, aryloxy groups such as p-tolyloxy groups, methoxycarbonyl groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acetoxy groups, propionyloxy groups, acyloxy groups such as benzoyloxy groups, acetyl groups, Aryl sulfani groups such as benzoyl groups, isobutyryl groups, acryloyl groups, methacryloyl groups, methacrylyl groups, and other acyl groups, methylsulfanyl groups, alkylsulfanyl groups such as tert-butylsulfanyl groups, phenylsulfanyl groups, and p-tolylsulfanyl groups Group, methylamino group, alkylamino group such as cyclohexylamino group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, arylamino group such as phenylamino group, p-tolylamino group, methyl group, In addition to alkyl groups such as ethyl group, tert-butyl group, dodecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, etc., 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 , Dimethylsulfoniumyl group, Phenyl phenacyl phosphonium Niu mill group, and the like.

  The specific oxime compound represented by the general formula (1) is more preferably a compound represented by the following general formula (2).

In the general formula (2), A represents a single bond or an alkylene group having 1 to 2 carbon atoms. X represents —CH ₂ —, —O—, —S—, —NR—, wherein R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ^1A and R ^1B each independently represent a hydrogen atom, an alkyl group or an aryl group. R ³ represents an acyl group or a sulfonyl group.
R ² , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, hydroxyl group, alkoxy group, aryloxy group, amino group, mercapto group, An alkylthio group or an arylthio group is shown.

Formula (2) in ^{R 1A, R 1B, R 3} , X and A, ^R 1A in the general formula ^(1), R ^1B, has the same meaning ^R 3, X and A, the preferred range is also the same .

The alkyl group, acyl group, alkoxy group, aryloxy group, amino group, alkylthio group, or arylthio group represented by R ² , R ⁴ , R ⁵ and R ⁶ in the general formula (2) further has a substituent. It may be.

The alkyl group which may have a substituent when R ² , R ⁴ , R ⁵ and R ⁶ represent an alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, and an alkyl group having 1 to 20 carbon atoms. Are more preferable, and an alkyl group having 1 to 10 carbon atoms is still more preferable.
Specifically, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, cyclopentyl Group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2-naphthoylmethyl group, allyl group, propargyl group and the like.

  Among the above specific examples, the alkyl group is preferably a methyl group, an isopropyl group, a t-butyl group, or a trifluoromethyl group.

The aryl group which may have a substituent when R ² , R ⁴ , R ⁵ and R ⁶ represent an aryl group is preferably an aromatic ring having 6 to 30 carbon atoms, and an aromatic ring having 6 to 20 carbon atoms. Is more preferable, and an aromatic ring having 6 to 10 carbon atoms is more preferable.
Specifically, for example, 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- Azulenyl group, 9-fluorenyl group, terphenyl group, o-, m-, and p-tolyl group, xinyl group, o-, m-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group Biphenylenyl, indacenyl, fluoranthenyl, acenaphthylenyl, fluorenyl, anthryl, bianthracenyl, teranthracenyl, anthraquinolyl, phenanthryl, triphenylenyl and the like.

  Among the above specific examples, a phenyl group, o-, m-, and p-tolyl group are more preferable, and an o-tolyl group is still more preferable.

Examples of the heterocyclic group in the case where R ² , R ⁴ , R ⁵ and R ⁶ represent a heterocyclic group include aromatic or aliphatic heterocyclic groups having a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. .
Specific examples include, for example, thienyl group, thianthenyl group, furyl group, pyranyl group, chromenyl group, xanthenyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl. Group, indolyl group, purinyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, quinoxanilyl group, 4aH-carbazolyl group, carbazolyl group, phenanthrolinyl group, isothiazolyl group, phenothiazinyl group, phenoxazinyl group, isochromanyl group, chromanyl Group, pyrrolidinyl group, imidazolidinyl group, imidazolinyl group, piperazinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group, and the like, such as carbazolyl group, thienyl group, pyridyl group, Group, pyranyl group, an imidazolyl group are preferable, thioxanthonyl group, a carbazolyl group, a thienyl group, a pyridyl group, a furyl group are more preferable.

When R ² , R ⁴ , R ⁵ and R ⁶ represent a halogen atom, examples of the halogen atom include fluorine, chlorine, bromine, iodine, etc., fluorine, chlorine, bromine are more preferable, and chlorine, bromine are further preferable.

When R ² , R ⁴ , R ⁵ and R ⁶ represent an alkoxy group, the alkoxy group which may have a substituent is preferably a methoxy group, an ethoxy group or a propyloxy group.

When R ² , R ⁴ , R ⁵ , and R ⁶ represent an alkylthio group, the alkylthio group that may have a substituent is preferably a methylthio group, an ethylthio group, or a propylthio group.
Among them, R ² , R ⁴ , R ⁵ and R ⁶ are preferably a hydrogen atom, an alkyl group, an alkoxy group, or an alkylthio group, and more preferably R ² , R ⁴ , R ⁵ and R Examples include a case where all of ⁶ are hydrogen atoms, or R ² or R ⁴ is a halogen atom, an alkyl group, an alkyloxy group, or an alkylthio group, and the others are hydrogen atoms.

Further, the specific oxime compound is preferably represented by the general formula (3).
As a result of the investigation, it was found that the compound represented by the following general formula (3) is a novel compound. The novel oxime compound having a structure represented by the following general formula (3) is extremely useful as a photopolymerization initiator as described in detail below.

In the general formula (3), R ^1A and R ^1B each independently represent a hydrogen atom, an alkyl group, or an aryl group. R ³ represents an acyl group or a sulfonyl group.
R ² , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, hydroxyl group, alkoxy group, aryloxy group, amino group, mercapto group Represents an alkylthio group or an arylthio group.
In the general formula (3), R ^1A , R ^1B , R ³ , R ² , R ⁴ , R ⁵ and R ⁶ are R ^1A , R ^1B , R ³ , R ² , R ⁴ , Synonymous with R ⁵ and R ⁶ .

As a preferable combination of these substituents, R ^1A is a hydrogen atom, R ^1B is a hydrogen atom, a methyl group, an ethyl group, or a phenyl group, R ³ is a methyl group, a t-butyl group, or a phenyl group, R ² and R ⁶ are each a hydrogen atom, and R ^{4 and} R ⁵ are each independently a hydrogen atom, a methoxy group, an ethoxy group, a phenyl group, a methylthio group, a phenylthio group, an acetyl group, a phenacyl group, a chlorine atom, or a bromine atom.

  The molar extinction coefficient at 365 nm of the specific oxime compound measured in ethyl acetate is preferably 50 to 30000, more preferably 100 to 10000, and further preferably 500 to 5000.

A general synthesis scheme of the novel compound represented by the general formula (3) is represented as follows.
That is, an oxime can be obtained by reacting a cyclic ketone having a methylene moiety at the α-position with a nitrite in the presence of a base. Moreover, the oxime ester compound represented by General formula (3) can be obtained by making this oxime react with a carboxylic acid chloride or a sulfonic acid chloride in presence of a base.
In the following formulae, R represents an acyl group or a sulfonyl group.

  Specific examples of the specific oxime compound of the present invention [Exemplary compounds (A-1) to (A-51)] are shown below, but the present invention is not limited thereto.

Among the exemplary compounds (A-1) to (A-51), from the viewpoint of the molar extinction coefficient at 365 nm, (A-3), (A-7), (A-13) to (A-26), (A-31) to (A-51) are more preferable.
More preferred compounds are (A-3), (A-7), and (A-13) to (A-25), (A-39), and (A-40).
Of the above exemplary compounds, exemplary compounds (A-3), (A-7), (A-13) to (A-26) and (A-31) to (A-51) listed as preferred compounds. Are all novel compounds represented by the general formula (3).

The specific oxime compound in the present invention has a maximum absorption wavelength in a 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, the absorbance at 365 nm and 405 nm is high.
The specific oxime compound described above has a molar extinction coefficient at 365 nm of 500 or more and 50000 or less. The molar extinction coefficient at 365 nm or 405 nm of the specific oxime compound is preferably 50 to 30000, more preferably 100 to 10000, and further preferably 500 to 5000 from the viewpoint of sensitivity.
Thus, the specific oxime compound has an absorption in a long wavelength region as compared with a conventional oxime compound. Therefore, when exposed with a light source of 365 nm or 405 nm, it exhibits excellent sensitivity, and the polymerizable composition of the present invention containing the specific oxime compound is cured with high sensitivity and excellent in film internal curability. I understand.

  The molar extinction coefficient of the specific oxime compound in this specification refers to a value measured at a concentration of 0.01 g / L using an ultraviolet-visible spectrophotometer (Carry-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent.

Among the specific oxime compounds according to the present invention, the oxime compound represented by the general formula (1) can be synthesized, for example, according to the scheme shown below, but is not limited to this method. X, Y, and R ³ in the following formula are as described above.
In the following scheme, the starting carboxylic acid may be a commercially available product. However, if there is no commercially available product as a suitable compound, a Williamson ether synthesis of a heteroaryl compound and a halogenated ester, or a heteroaryl compound It can be easily synthesized by a Michael addition reaction with an acrylate derivative followed by hydrolysis using sodium hydroxide or the like.
The acylation cyclization using an acid is completed by heating and stirring at 95 ° C. in methanesulfonic acid. Cyclization proceeds efficiently if it is a 5- to 7-membered ring. In the oximation, an oxime can be obtained by reacting with a nitrite at 0 ° C. in the presence of a base. The oxime can be reacted with carboxylic acid chloride or sulfonic acid chloride in the presence of a base at 0 ° C. to room temperature to obtain the corresponding oxime ester.

In addition to the polymerizable composition of the present invention described above, the specific oxime compound in the present invention can be applied to curable materials for the following uses by utilizing the photopolymerization initiation function.
That is, for example, printing ink materials exemplified below (for example, for screen printing inks, offset or flexographic printing inks, for UV curable inks), white or colored finishing materials for wood or metal, powder coating materials (in particular, Printing materials that can be developed with holographic recording materials, image recording materials, organic solvents or aqueous alkali, for paper, wood, metal or plastic coating materials), building markings, road marking materials, and photographic reproduction techniques. For original recording layer materials, sun curable coating materials for the production of screen printing masks, dental filling compositions, adhesives, pressure sensitive adhesives, laminating resin materials, for both liquid and dry thin film etching resists Materials, solder resist materials, electroplating resist materials Materials for permanent resists, optically configurable dielectric materials for printed circuit boards and electronic circuits, various display materials, optical switch materials, optical grating (interference grating) forming materials, optical circuit manufacturing materials, large quantities Materials for manufacturing three-dimensional articles by curing (UV curing in transparent molds) or stereolithographic techniques (eg materials as described in US Pat. No. 4,575,330), composite materials (For example, if desired, styrenic polyester that may include glass fibers and / or other fibers and other auxiliaries) For coating or sealing materials for manufacturing other thick layer compositions, electronic components and integrated circuits Resist materials, optical fiber forming materials, coating materials for manufacturing optical lenses (eg contact lenses or Fresnel lenses), Various kinds of materials for manufacturing medical devices, auxiliary tools or implants, and materials for producing gels having thermotropic properties as described in German Patent No. 19,700,064 and European Patent No. 678,534, for example Can be used.

  The specific oxime compound according to the present invention functions as a radical initiator when, for example, the oxime ester is composed of an acyl group. For example, when the oxime ester is composed of a sulfonyl group, energy rays, particularly light. It is also possible to generate an acid by irradiation. 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 resist materials for semiconductor manufacturing, TFT manufacturing, color filter manufacturing, micromachine component manufacturing, etc. using a decomposition reaction catalyzed by the generated acid. it can.

  As described above, since the specific oxime compound according to the present invention can be used as a photopolymerization initiator, (B) a polymerizable composition that is polymerized and cured by light when used in combination with the polymerizable compound (the present invention). It is preferable to apply to the polymerizable composition.

The photopolymerizable composition of the present invention comprises the above-mentioned (A) specific oxime compound and the (B) polymerizable compound described later. Depending on the function of the (A) specific oxime compound, the wavelength is 365 nm or 405 nm. It is possible to form a cured film that has high sensitivity to light, is excellent in storage stability, and can suppress coloring due to aging. Although this detailed mechanism is unknown, the (A) specific oxime compound according to the present invention absorbs light and radical recombination when cleaved is suppressed due to its molecular structure. It is thought that the amount can be increased and the sensitivity can be increased. Moreover, since radical recombination is suppressed, it is considered that the reaction between the decomposition products of the specific oxime compound is suppressed during heating and the coloration derived from the reaction is suppressed.
That is, according to the compound of the present invention in which a carbonyl group is present at the α-position of the imino group, the imino radical that is a coloring factor is subsequently decomposed to nitrile, so that coloring after exposure is suppressed. Further, the decomposition efficiency of imino radicals is improved by cyclization, and the recombination of radicals is efficiently suppressed, so that it is considered effective for suppressing coloring.

In the present invention, the color difference ΔEab ^* may be used in order to evaluate the coloration of the cured film formed from the polymerizable composition of the present invention 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 polymerizable composition of the present invention was subjected 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 amounts in the range of 10mJ ^/ cm ² ~2,500mJ ^/ cm 2 at 365 nm), 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.

  Hereinafter, the photopolymerizable composition of the present invention can be suitably used for forming a colored region of a color filter or the like (1) [hereinafter referred to as a photopolymerizable composition for a color filter as appropriate. ) And a polymerizable composition (2) that can be suitably used for forming a photosensitive layer of a lithographic printing plate precursor, etc., will be described in detail. The use of the polymerizable composition of the present invention is as described above. However, it is not limited to these.

-Polymerizable composition (1)-(Photopolymerizable composition for color filter)
Since the photopolymerizable composition for a color filter is used for the purpose of forming a colored region used for a color filter, (A) a specific oxime compound. (B) In addition to the polymerizable compound, it contains (C) a colorant. Hereinafter, each component which comprises the photopolymerizable composition for color filters is described.
[(1)-(A) specific oxime compound]
The (A) specific oxime compound contained in the polymerizable composition (1) functions as a polymerization initiator in the composition. (A) Details of the specific oxime compound are as described above.
The content of the specific oxime compound in the polymerizable composition (1) is preferably 0.5 to 40% by mass, more preferably 1 to 35% by mass, and more preferably 1.5 to 30% by mass with respect to the total solid content of the composition. % Is more preferable.
A specific oxime compound may be used individually by 1 type, and may use 2 or more types together.

(Other photopolymerization initiators)
The polymerizable composition (1) may be used in combination with a known photopolymerization initiator other than the specific oxime compound as long as the effects of the present invention are not impaired. In this case, it is preferable to use a known photopolymerization initiator in a range of 50% by mass or less of the specific oxime compound.
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 polymerizable composition (1) is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond, preferably 2 It is selected from compounds having at least one. 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.

  Preferred examples of the polymerizable compound (1)-(B) that can be suitably used in the present invention include compounds described in paragraphs [0056] to [0078] of JP-A-2008-224982.

  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. )

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.

0.1-30 mass% is preferable with respect to the total solid of this composition, as for content of the polymeric compound in polymeric composition (1), 0.2-20 mass% is more preferable, 0.3- 15 mass% is still more preferable.
A polymeric compound may be used individually by 1 type, and may use 2 or more types together.

[(1)-(C) Colorant]
The polymerizable composition (1) can contain a colorant (C). By containing a colorant, a colored polymerizable composition having a desired color can be obtained.
In addition, since the polymerizable composition (1) contains the specific oxime compound which is a polymerization initiator (A) of the present invention having excellent sensitivity to a 365 nm or 405 nm light source which is a short wavelength light source, Even when contained in a high concentration, it can be cured with high sensitivity.

The colorant used in the polymerizable composition (1) is not particularly limited, and various conventionally known dyes and pigments can be used singly or in combination, and these can be used as a photopolymerizable composition. It is appropriately selected according to the use of the product. If the photopolymerizable composition of the present invention is used for color filter production, chromatic colorants (chromatic colorants) such as R, G, and B that form color pixels of the color filter, and a black matrix Any of the black colorants (black colorants) commonly used for formation can be used.
Since the photopolymerizable composition of the present invention containing the (A) specific oxime compound can be cured with high sensitivity even if the exposure amount is small, the photopolymerizable composition containing a black colorant that hardly transmits light. It can be particularly preferably used for the composition.

Hereinafter, the colorant applicable to the polymerizable composition (1) will be described in detail using 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.

  Examples of the organic pigment include those described in paragraphs [0030] to [0036] and [0039] to [0048] of JP-A-2008-224982, as well as C.I. I. Pigment green 58, C.I. I. Pigment blue 79 in which Cl is replaced with OH.

  In the present invention, those having a basic nitrogen atom in the structural formula of the pigment can be preferably used. These pigments having a basic nitrogen atom exhibit good dispersibility in the polymerizable 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.

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 red pigment to the yellow pigment is preferably 100: 5 to 100: 50. By setting it as the said range, color purity can be improved and the adaptation to a NST target hue becomes favorable.
In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. 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. By setting the mass ratio of the green pigment to the yellow pigment in the above range where 100: 5 to 100: 150 is preferable, the color purity can be improved, and the NST target hue can be suitably matched.
The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

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 the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

  Further, as the pigment for the black matrix, carbon, titanium carbon, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium carbon is preferable. The mass ratio of carbon to titanium carbon is preferably in the range of 100: 0 to 100: 60 from the viewpoint of dispersion stability.

  Titanium black can also be used as a black matrix pigment. The titanium black dispersion is described in detail below.

The titanium black dispersion is a dispersion containing titanium black as a coloring material.
By including titanium black in the polymerizable composition as a titanium black dispersion prepared in advance, the dispersibility and dispersion stability of titanium black are improved.
Hereinafter, titanium black will be described.

-Titanium black-
Titanium black that can be used in the present invention is black particles having titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and can also be treated with a water repellent material as disclosed in JP-A-2007-302836. .

  Titanium black is produced by heating a mixture of titanium dioxide and metal titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, No. 61-201610), and a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610). It is not a thing.

  The particle size of the titanium black particles is not particularly limited, but is preferably 3 to 2000 nm, more preferably 10 to 500 nm, and still more preferably 20 to 200 nm from the viewpoint of dispersibility and colorability. .

The specific surface area of the titanium black is not particularly limited, but the water repellency after the surface treatment of the titanium black with a water repellent agent has a predetermined performance. Therefore, the value measured by the BET method is usually 5 to 150 m. ² / g approximately, and preferably from 20 to 100 m ² / g approximately.

  Examples of commercially available titanium black include, for example, Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, Ako Kasei Co., Ltd., Tilac D, manufactured by Mitsubishi Materials Corporation. However, the present invention is not limited to these.

In the polymerizable 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 polymerizable composition (1) is not particularly limited, and conventionally known dyes for color filters 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.

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. Acid dyes such as Solvent orange 45; Rhodamine B, Rhodamine 110 and derivatives of these dyes are also preferably used.

  Among them, as the colorant, triallylmethane, 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 polymerizable composition (1) is preferably a dye or a pigment. In particular, a pigment having an average particle size (r) of 20 nm ≦ r ≦ 300 nm, preferably 125 nm ≦ r ≦ 250 nm, particularly preferably 30 nm ≦ r ≦ 200 nm 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 polymerizable composition (1), it is preferable that it is 30 mass%-95 mass% in the total solid of a photopolymerizable composition, and 40 mass%-90 mass%. Is more preferable, and 50 mass%-80 mass% is still more preferable.
By setting the content of the colorant in the above range, an appropriate chromaticity can be obtained when a color filter is produced from the polymerizable composition (1). Further, since photocuring sufficiently proceeds and the strength as a film can be maintained, it is possible to prevent the development latitude during alkali development from becoming narrow.
That is, since the specific oxime compound (A) which is a polymerization initiator in the present invention has high light absorption efficiency, it is highly sensitive even when it contains a colorant in a high concentration in the photopolymerizable composition. It can be polymerized and cured, and the effect of improving sensitivity is remarkably exhibited as compared with the case where other polymerization initiators are used.

[(1)-(D) Pigment dispersant]
When the polymerizable composition (1) contains a pigment such as titanium black or an organic pigment as the (C) colorant, (D) a pigment dispersant may be added from the viewpoint of improving the dispersibility of the pigment. preferable.

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 mentioned 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 type), EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (azo) "Adisper PB821, PB822" manufactured by Ajinomoto Fan Techno Co., "Floren TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., "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” manufactured by Enomoto Kasei Co., Ltd., Kao “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) ”,“ acetamine 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 Chemicals, and the like.

  These pigment 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 (D) pigment dispersant in polymeric composition (1), it is preferable that it is 1-80 mass parts with respect to 100 mass parts of pigments which are (C) colorants, and 5-70 masses. Part is more preferable, and it is still more preferable that it is 10-60 mass parts.
Specifically, if a polymer dispersant is used, the amount used is preferably in the range of 5 to 100 parts in terms of mass, and in the range of 10 to 80 parts, with respect to 100 parts by mass of the pigment. It is more preferable.
Moreover, when using together a pigment derivative, it is preferable that it is in the range of 1-30 parts in conversion of mass as a usage-amount of a pigment derivative, and is in the range of 3-20 parts with respect to 100 mass parts of pigments. A range of 5 to 15 parts is particularly preferable.

  In the polymerizable composition (1), when (C) a pigment as a colorant is used and (D) a pigment dispersant is further used, the total content of the colorant and the dispersant is from the viewpoint of curing sensitivity and color density. However, 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 more preferably 50% by mass or more and 80% by mass with respect to the total solid content constituting the polymerizable composition. % Or less is more preferable.

As long as the polymerizable composition (1) does not impair the effects of the present invention, the polymerizable composition (1) may further contain optional components detailed below.
Hereinafter, the optional components that can be contained in the polymerizable composition (1) will be described.

[(1) -sensitizer]
The polymerizable composition (1) may contain a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and increasing the photosensitive wavelength.
The sensitizer that can be used in the present invention is preferably a sensitizer that sensitizes the above-mentioned (A) specific oxime compound by an electron transfer mechanism or an energy transfer mechanism.

Examples of the sensitizer used in the polymerizable composition (1) include compounds described in paragraph numbers [0101] to [0154] of JP-A-2008-32803.
The content of the sensitizer in the polymerizable composition (1) is preferably 0.1% by mass 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 mass% to 15 mass% is more preferable.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

[(1) -Co-sensitizer]
The polymerizable composition (1) preferably further contains a cosensitizer.
In the present invention, the co-sensitizer further enhances the sensitivity of (A) the specific oxime compound and the sensitizer to actinic radiation, or suppresses the inhibition of polymerization of (B) the polymerizable compound by oxygen. Have.

  Examples of such co-sensitizers include compounds described in paragraph numbers [0176] to [0178] of JP-A-2008-32803.

  The content of these co-sensitizers is 0.1% by mass to 30% with respect to the mass of the total solid content of the polymerizable composition (1) from the viewpoint of improving the curing rate due to the balance between the polymerization growth rate and the chain transfer. The range of mass% is preferable, the range of 1 mass% to 25 mass% is more preferable, and the range of 0.5 mass% to 20 mass% is still more preferable.

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

In the general formula (IV), X represents a sulfur atom, an oxygen atom, or —N (R ⁴³ ) —, and R ⁴³ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 6 to 13 carbon atoms. 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, the thiol compound suitable for the polymerizable composition (1) is preferably represented by the following general formula (V). Such compounds are described in detail in paragraphs [0018] to [0043] of JP-A-2008-32803, and the compounds described herein can be applied to the present invention.

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

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 of the general formulas described above may be used in combination, or compounds represented by different general formulas may be used in combination.

  When the polymerizable composition (1) contains a thiol compound, the content thereof is from the viewpoint of improving the curing rate due to the balance between the polymerization growth rate and chain transfer, with respect to the total solid content of the polymerizable composition. The range of 0.5% by mass to 30% by mass is preferable, the range of 1% by mass to 25% by mass is more preferable, and the range of 3% by mass to 20% by mass is more preferable.

[(1) -Binder polymer]
In the polymerizable 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 a linear organic polymer include the compounds described in paragraphs [0166] to [0175] of JP-A-2008-32803, and these can also be applied to the present invention.
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.

The weight average molecular weight of the binder polymer that can be used in the polymerizable composition (1) is preferably 5,000 or more, more preferably in the range of 10,000 to 300,000, and the number average molecular weight is preferably 1 2,000 or more, and more preferably in the range of 2,000 to 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 content of the binder polymer is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, and still more preferably 1 to 20% by mass in the total solid content of the polymerizable composition (1).

[(1) -polymerization inhibitor]
In the polymerizable composition (1), it is desirable to add a small amount of a thermal polymerization inhibitor to prevent unnecessary thermal polymerization of the polymerizable compound (B) during the production or storage of the polymerizable composition. .
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% by mass to about 5% by mass with respect to the total solid content of the polymerizable 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 about 0.5% by mass to about 10% by mass of the total composition.

[(1) -Adhesion improver]
In polymeric composition (1), in order to improve adhesiveness with hard surfaces, such as a support body of the formed cured film, an adhesion improving agent can be added. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.

Examples of the silane coupling agent include compounds described in paragraph [0185] of JP-A-2008-32803.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-amino Propyltriethoxysilane and phenyltrimethoxysilane are preferred, and γ-methacryloxypropyltrimethoxysilane is most preferred.
The addition amount of the adhesion improver is preferably 0.5% by mass to 30% by mass and more preferably 0.7% by mass to 20% by mass in the total solid content of the polymerizable composition (1).

[(1)-Diluent]
The polymerizable composition (1) may use various organic solvents as a diluent.
Examples of the organic solvent used here include various solvents described in paragraph No. [0187] of JP-A-2008-32803.
These solvents can be used alone or in combination.
The concentration of the solid content with respect to the organic solvent in the polymerizable composition of the present invention is preferably 2% by mass to 60% by mass.

[(1)-Other additives]
Furthermore, in order to improve the physical property of a cured film, you may add well-known additives, such as an inorganic filler, a plasticizer, a fat-sensitizing agent, with respect to polymeric 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 polymerizable composition (1) contains the specific oxime compound (A), it is cured with high sensitivity, has good storage stability, and further suppresses coloring when heated with aging. be able to. In addition, when the polymerizable composition (1) is applied to the surface of a hard material and cured, it exhibits high adhesion to the surface.
Such a polymerizable composition (1) can form a pattern with high sensitivity even when it contains a large amount of a colorant, has excellent adhesion to the substrate, and the formed colored cured film is repeatedly formed. Since coloring and discoloration are suppressed even when heated or irradiated with light, it is particularly useful for forming a colored region of a color filter. The polymerizable composition (1) of the present invention is used for light for color filters. It is preferable to use it as a polymerizable composition.

-Polymerizable composition (2)-[Photopolymerizable composition for photosensitive lithographic printing plate precursor]
The photopolymerizable composition of the present invention is useful for forming a photosensitive layer of a lithographic printing plate precursor because an exposed region is cured with high sensitivity by pattern exposure to form a firm film.
Hereinafter, preferred embodiments in the case of applying the photopolymerizable composition of the present invention to the photosensitive layer of a lithographic printing plate precursor will be described.
[(2)-(A) Specific oxime compound]
The specific oxime compound contained in the polymerizable composition (2) can function as a polymerization initiator in the composition. The specific oxime compound (A) in this embodiment is as described above.
The content of the (A) specific oxime compound in the polymerizable composition (2) is preferably 0.5% by mass to 40% by mass and more preferably 1% by mass to 35% by mass with respect to the total solid content of the composition. 1.5 mass% to 30 mass% is more preferable.
A specific oxime compound may be used individually by 1 type, and may use 2 or more types together.

(Other polymerization initiators)
Also in the polymerizable composition (2), other known polymerization initiators other than the specific 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]
As the polymerizable compound (B) contained in the polymerizable composition (2), the addition polymerizable compounds described above in the polymerizable composition (1) can be mentioned as preferable examples.

  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. With regard to the compounding ratio of the addition polymerizable compound in the photosensitive layer, a larger amount is advantageous in terms of sensitivity, but if it is too much, 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 the developer may occur.

From these viewpoints, the content of the addition polymerizable compound is preferably 5% by mass to 80% by mass, more preferably 25% by mass to 75% by mass with respect to the total solid content of the polymerizable 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)-Binder polymer]
The polymerizable 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. As such a “linear organic polymer”, for example, a compound described as “(E) binder” in paragraphs [0130] to [0137] of JP-A-2009-86338 can be used.

  Among these binder polymers, in particular, benzyl (meth) acrylate / (meth) acrylic acid / a copolymer containing other addition-polymerizable vinyl monomer as required, and allyl (meth) acrylate / (meth) acrylic acid / A copolymer containing other addition-polymerizable vinyl monomers as required is preferable because it is excellent in the balance of film strength, sensitivity, and developability.

  The binder polymer can be mixed in the polymerizable composition (2) in an arbitrary amount. From the standpoint of image intensity and the like, it is preferably in the range of 30% by mass 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 is substantially insoluble in water and 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 meq / g to 3.0 meq / g, and the preferred molecular weight is in the range of 3,000 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) -sensitizer]
It is preferable that polymeric composition (2) contains a sensitizer with polymerization initiators, such as (A) specific 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.

  Examples of the sensitizer that can be applied to the polymerizable composition (2) include those already described in the description of the polymerizable 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 polymerizable composition (2) is 100: 0 to 1:99, more preferably 90:10 to 10:90, and most preferably 80:20. ~ 20: 80.

[(2) -Co-sensitizer]
To the polymerizable composition (2), a known compound having an effect of 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 description of the polymerizable composition (1). In addition to these, phosphorus compounds (such as diethyl phosphite) described in JP-A-6-250387 are also included.

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

[(2)-Polymerization inhibitor]
The polymerizable 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)-(C) Colorant]
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. Many dyes cause a decrease in the sensitivity of the photopolymerization type photosensitive layer, so that 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)-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.
The lithographic printing plate precursor according to the invention is obtained by applying such a polymerizable composition (2) onto a support to form a photosensitive layer. The planographic printing plate precursor of the present invention will be described later.

As the polymerizable composition (1) and the polymerizable composition (2), preferred applications of the polymerizable composition of the present invention and typical compositions suitable for the respective applications have been described. The use of the composition is not limited to these, and is suitably used for various materials that are polymerized and cured. Depending on the design, the addition amount of the components and other additives are used by adjusting the type and amount. It is done.
Other uses include, for example, molding resins, casting resins, stereolithography resins, sealants, dental polymer materials, printing inks, paints, photosensitive resins for printing plates, color proofs for printing, and light for color filters. Polymerizable 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, adhesive , Pressure-sensitive adhesives, adhesives, release coating agents and the like, and can be used for these various applications.

[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 color filters of the present invention [the polymerizable composition (1)].
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 includes a step of applying a photopolymerizable composition for a color filter of the present invention [the polymerizable composition (1)] to form a colored polymerizable composition layer on a support. (Hereinafter abbreviated as “polymerizable composition layer forming step” as appropriate), a step of exposing the polymerizable composition layer in a pattern (hereinafter abbreviated as “exposure step” as appropriate), and exposure. And a step of developing the subsequent polymerizable composition layer to remove unexposed portions and forming 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 polymerizable composition layer (polymerizable composition). Layer formation step), exposing through a predetermined mask pattern, curing only the light-irradiated coating film portion (exposure step), and developing with a developer (development step), each color (three colors or four colors) ) Can be formed to produce the color filter of the present invention.
Hereinafter, each process in the manufacturing method of the color filter of this invention is demonstrated.

[Polymerizable composition layer forming step]
In the polymerizable composition layer forming step, a layer made of a colored polymerizable composition is formed by applying 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 -40 μm to 1.0 μm is more preferable.

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

[Exposure process]
In the exposure step, the polymerizable composition layer formed in the polymerizable composition layer forming step is exposed in a pattern, pattern exposure is usually performed through a mask and only the coating film portion irradiated with light is exposed. Although it is performed by a curing method, pattern exposure by scanning exposure may be divided depending on the purpose.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-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 seconds 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. ] An alkaline aqueous solution obtained by diluting an organic alkaline compound such as -7-undecene with pure water so as to have a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass. 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 colored polymerizable composition layer forming step, exposure step, and development step, 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.

[Solid-state imaging device]
The solid-state imaging device of the present invention includes the color filter of the present invention.
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 polymerizable composition (2) according to the invention on a support.
In order to form a printing plate using the lithographic printing plate precursor of the present invention, the polymerizable composition (2) of the present invention is applied directly or via another layer onto a lithographic printing plate support, A photopolymerizable composition layer is formed to obtain a lithographic printing plate precursor, and the photosensitive layer of the lithographic printing plate precursor is exposed in a pattern to cure only the exposed portion and develop the unexposed area with a developer. By doing so, the remaining photosensitive layer becomes an ink-receiving layer for printing, and the region where the photosensitive layer is removed and the hydrophilic support is exposed becomes a receiving region for dampening water, whereby a lithographic printing plate can be obtained.
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 present invention contains a polymerizable composition according to the present invention in the photosensitive layer, so that it has high sensitivity and is excellent in stability with time and printing durability. 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 polymerizable composition (2), which is one of the preferred embodiments of the photopolymerizable composition of the present invention, is replaced with 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. As a solvent used here, it can select from the solvent disclosed as a diluent in the said polymeric compound (1) suitably, and can use it.
These solvents can be used alone or in combination. The solid content in the coating solution is suitably 2 to 50% by mass.

The amount of the photosensitive layer applied to the support 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, when the amount is too large, the sensitivity is lowered, it takes time for the exposure, and a longer time is required for the development processing.
The photosensitive layer for the main purpose is the planographic printing plate precursor for scanning exposure of the present invention, the coating amount of mass in the range of 0.1g ^/ m ² ~10g / m 2 after drying is 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.
As the support, for example, those described in paragraph numbers [0143] to [0148] of JP-A-2009-86338 can be used.
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. Such an aluminum plate is preferably subjected to anodizing treatment and hydrophilic treatment as described in the above publication.

[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.
As such a protective layer, those described in paragraph numbers [0163] to [0165] of JP-A-2009-86338 can be appropriately selected and used.

  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, a compound having a relatively strong interaction with the substrate, such as a compound having a diazonium structure or a phosphone compound, is added to the photosensitive layer, or an undercoat layer containing these compounds is provided between the support and the photosensitive layer. As a result, the adhesion between the support and the photosensitive layer is improved, and the printing durability can be increased.
On the other hand, by adding a hydrophilic polymer such as polyacrylic acid or polysulfonic acid to the photosensitive layer or providing an undercoat layer containing these compounds, the developability of the non-image area is improved and the stain resistance is improved. Can be improved.

[Plate making]
A lithographic printing plate precursor is usually subjected to image exposure, the photosensitive layer in the exposed portion is cured, and then the unexposed portion of the photosensitive layer is removed with a developer to form an image, whereby a lithographic printing plate is obtained. .

As the exposure method applicable to the lithographic printing plate precursor according to the invention, a known method can be used without limitation. In the present invention, since the specific oxime compound (A) is used as the photo-fifteen initiator, the wavelength of the desired exposure light source is 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, it can be applied to a so-called on-press development method in which printing can be performed without performing wet development, such as exposure-development on the press.

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 (YVO4) and SHG crystal x 2 times (355 nm, 5 mW to 1 W), combination of Cr: LiSAF and SHG crystal (430 nm, 10 mW), as a semiconductor laser system, KNbO ₃ ring resonator (430 nm, 30 mW), Combination of waveguide type wavelength conversion element and AlGaAs / InGaAs semiconductor (380 nm to 450 nm, 5 mW to 100 mW), combination of waveguide type wavelength conversion element and AlGaInP, AlGaAs semiconductor (300 nm to 350 nm, 5 mW to 1) 0mW), AlGaInN (350nm~450nm, 5mW~30mW ), other, _{N 2} laser (337 nm as a pulse laser, pulse: 0.1 to 10), XeF (351 nm, pulse 10 to 250 mJ), 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.

  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 mass% to 10 mass%, preferably 0.5 mass% to 5 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.

  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 the temperature 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 in the range of 200 ° C to 500 ° C. When the temperature is 200 ° C. or higher, sufficient image strengthening action can be obtained. When the temperature is 500 ° C. or lower, problems such as deterioration of the support and thermal decomposition of the image portion do not occur.

  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. Unless otherwise specified, “part” is based on mass, and “%” is “mass%”.

  First, the detail of the specific oxime compound (specific compound 1-specific compound 9) used for an Example and the comparative compound (comparative compound 1-comparative compound 4) used for a comparative example is shown.

  Specific compounds 1 to 9 which are specific oxime compounds in the above list were synthesized by the following method.

(Synthesis Example 1: Synthesis of specific compound 1 which is a specific oxime compound)
α-Tetralone (5.0 g, 34.2 mmol) was suspended in THF and cooled to 0 ° C. To this suspension was added t-butoxypotassium (4.22 g, 37.6 mmol), and the mixture was stirred at 0 ° C. for 30 minutes. Meanwhile, the reaction solution became dark blue and dissolved. Isopentyl nitrate (4.4 g, 37.6 mmol) was added dropwise at 0 ° C. over 10 minutes, and the mixture was further stirred for 1 hour. After extraction with ethyl acetate and washing with a saturated aqueous sodium chloride solution, dehydration and decolorization operations were performed with magnesium sulfate and activated carbon. The organic layer was concentrated and purified by column chromatography (hexane / ethyl acetate = 1/1) to obtain 1.83 g of α-tetralone-2-oxime.
α-Tetralone-2-oxime (0.75 g, 4.3 mmol) was dissolved in 10 ml of acetone, cooled to 0 ° C., triethylamine (0.65 g, 6.4 mmol) was added, and acetic anhydride (0.65 g, 6.4 mmol) was added. The mixture was further warmed to room temperature and stirred for 2 hours. The reaction mixture was extracted with ethyl acetate, washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the organic layer was concentrated. The specific compound 1 (yield 0.56 g) was obtained by column chromatography (hexane / ethyl acetate = 2/1).

The structure of the obtained specific compound 1 was identified by NMR.
(1H-NMR 300 MHz deuterated chloroform): 8.14 (d, 1H, J = 7.5), 7.58 (t, 1H, J = 7.8 Hz), 7.41 (t, 1H, J = 7) .8 Hz), 7.31 (d, 1 H, J = 7.5 Hz)), 3.24 (t, 2 H, J = 7.2 Hz) 3.12 (t, 2 H, J = 7.2 Hz), 2 .35 (s, 3H)
When the molar extinction coefficient at 365 nm of the specific compound 1 was measured by the method described above, it was 150 in ethyl acetate.

(Synthesis Example 2: Synthesis of specific compound 2 which is a specific oxime compound)
1-Indanone (10.0 g, 75.7 mmol) was suspended in 100 mL of THF and cooled to 0 ° C. To this suspension was added t-butoxypotassium (9.3 g, 83.3 mmol), and the mixture was stirred at 0 ° C. for 30 minutes. Meanwhile, the reaction solution became dark blue and dissolved. Isopentyl nitrate (9.8 g, 83.3 mmol) was added dropwise at 0 ° C. over 10 minutes, and the mixture was further stirred for 1 hour. After extraction with ethyl acetate and washing with a saturated aqueous sodium chloride solution, dehydration and decolorization operations were performed with magnesium sulfate and activated carbon. The organic layer was concentrated and purified by column chromatography (hexane / ethyl acetate = 1/1) to obtain 4.3 g of indan-1-one-2-oxime.
Indan-1-one-2-oxime (2.0 g, 12.4 mmol) was dissolved in 20 ml of acetone, cooled to 0 ° C., triethylamine (1.88 g, 18.6 mmol) was added, and acetic anhydride (1 .90 g, 18.6 mmol) was added. The mixture was further warmed to room temperature and stirred for 2 hours. The reaction mixture was extracted with ethyl acetate, washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the organic layer was concentrated. The specific compound 2 (yield 0.65 g) was obtained by column chromatography (hexane / ethyl acetate = 2/1).

The structure of the obtained specific compound 2 was identified by NMR.
(1H-NMR 300 MHz deuterated chloroform): 7.92 (d, 1H, J = 7.8 Hz), 7.71 (t, 1H, J = 7.8 Hz), 7.55-7.46 (m, 2H) ), 3.97 (s, 2H) 2.36 (s, 3H).
When the molar extinction coefficient at 365 nm of the specific compound 2 was measured in the same manner as described above, it was 170 in ethyl acetate.

(Synthesis Example 3: Synthesis of specific compound 4 which is a specific oxime compound)
Compound A (10.0 g, 47.0 mmol) and isopentyl nitrite (6.1 g, 51.7 mmol) were suspended in 30 mL of ethanol and cooled to 0 ° C. To this was added dropwise a solution of potassium hydroxide (85%, 2.7 g, 40.4 mmol) and ethanol 45 mL over 45 minutes. The reaction solution turned yellow and dissolved. The mixture was stirred at 0 ° C. for 2 hours, extracted with ethyl acetate, washed with a saturated aqueous ammonium chloride solution and distilled water, dehydrated with magnesium sulfate, and the organic layer was concentrated. Further, recrystallization from hexane / ethyl acetate gave Compound C (yield: 4.0 g).
Compound C (1.5 g, 6.2 mmol) is dissolved in 20 mL of THF, cooled to 0 ° C., and acetyl chloride (0.73 g, 9.3 mmol) and pyridine (0.54 g, 6.8 mmol) are added. -Dimethylaminopyridine (0.08 g, 0.62 mmol) was added. The mixture was warmed to room temperature and stirred for 2 hours. The reaction solution was crystallized from 200 mL of distilled water, and then reslurried with methanol at 0 ° C. to obtain the specific compound 4 (yield 1.5 g).

The structure of the obtained specific compound 4 was identified by NMR.
(1H-NMR 300 MHz deuterated chloroform): 8.12 (s, 1H), 7.46 (d, 1H, J = 7.8 Hz), 7.26 (d, 1H, J = 7.8 Hz), 4. 89 (q, 1H, J = 7.2 Hz), 2.35 (s, 3H), 1.64 (d, 3H, J = 7.2 Hz).
When the molar extinction coefficient at 365 nm of the specific compound 4 was measured by the method described above, it was 1070 in ethyl acetate.

(Synthesis Example 4: Synthesis of Specific Compound 3 which is a Specific Oxime Compound)
Synthesis was performed in the same manner as in Synthesis Example 3 except that the following compound D (10.0) g was used instead of compound A, and specific compound 3 (yield 5) was obtained using compound E (6.5 g) as an intermediate. .2 g) was obtained.

The structure of the obtained specific compound 3 was identified by NMR.
(1H-NMR 300 MHz deuterated chloroform): 7.63 (s, 1H), 7.20 (d, 1H, J = 8.7 Hz), 7.09 (d, 1H, J = 8.7 Hz), 4. 85 (q, 1H, J = 7.2 Hz), 3.85 (s, 3H), 2.34 (s, 3H), 1.64 (d, 3H, J = 7.2 Hz).
When the molar extinction coefficient at 365 nm of the specific compound 3 was measured by the method described above, it was 650 in ethyl acetate.

(Synthesis Example 5: Synthesis of specific compound 6 which is a specific oxime compound)
The specific compound 6 (yield 3.) was synthesized by the same procedure as in Synthesis Example 3 except that the following compound F (6.3 g) was used instead of the compound A, and the compound G (4.6 g) was used as an intermediate. 1 g) was obtained.

The structure of the obtained specific compound 6 was identified by NMR.
(1H-NMR 300 MHz deuterated chloroform): 8.15 (d, 1H, J = 8.1 Hz), 7.52 (t, 1H, J = 8.1 Hz), 7.30 (m, 2H), 4. 87 (q, 1H, J = 7.2 Hz), 2.35 (s, 3H), 1.64 (d, 3H, J = 7.2 Hz).
When the molar extinction coefficient at 365 nm of the specific compound 6 was measured by the method described above, it was 1530 in ethyl acetate.

(Synthesis Example 6: Synthesis of specific compound 7 which is a specific oxime compound)
The specific compound 7 (yield 4.5 g) was obtained by synthesizing in the same manner as in Synthesis Example 3 except that the following compound H (5.7 g) was used instead of compound A, and using compound J (5.0 g) as an intermediate. )

The structure of the obtained specific compound 7 was identified by NMR.
(1H-NMR 300 MHz deuterated chloroform): 8.12 (d, 1H, J = 9.0 Hz), 6.81 (d, 1H, J = 9.0 Hz), 6.73 (s, 1H), 4. 85 (q, 1H, J = 7.2 Hz), 3.88 (s, 3H), 2.34 (s, 3H), 1.64 (d, 3H, J = 7.2 Hz).
When the molar extinction coefficient at 365 nm of the specific compound 7 was measured by the method described above, it was 2300 in ethyl acetate.

(Synthesis Example 7: Synthesis of specific compound 8 which is a specific oxime compound)
Intermediate C (4.1 g) was synthesized using Compound A, and synthesized in the same manner as in Synthesis Example 3 except that benzoyl chloride was used instead of acetyl chloride, and specific compound 8 (yield 3.9 g) was obtained. Got.

The structure of the obtained specific compound 8 was identified by NMR.
(1H-NMR 300 MHz deuterated chloroform): 8.12 (s, 1H), 7.4-7.0 (m, 7H), 4.89 (q, 1H, J = 7.2 Hz), 1.64 ( d, 3H, J = 7.2 Hz).
When the molar extinction coefficient at 365 nm of the specific compound 8 was measured by the method described above, it was 1710 in ethyl acetate.

(Synthesis Example 8: Synthesis of specific compound 9 which is a specific oxime compound)
Intermediate C (6.3 g) was synthesized using Compound A, and synthesized in the same manner as in Synthesis Example 3 except that pivaloyl chloride was used instead of acetyl chloride, and specific compound 9 (yield 5. 9 g) was obtained.

The structure of the obtained specific compound 9 was identified by NMR.
(1H-NMR 300 MHz deuterated chloroform): 8.12 (s, 1H), 7.46 (d, 1H, J = 7.8 Hz), 7.26 (d, 1H, J = 7.8 Hz), 4. 89 (q, 1H, J = 7.2 Hz), 1.64 (d, 3H, J = 7.2 Hz), 1.30 (s, 9H).
When the molar extinction coefficient at 365 nm of the specific compound 9 was measured by the above-described method, it was 1670 in ethyl acetate.
In addition, it carried out similarly to said synthesis example 1-synthesis example 8, and synthesize | combined the specific compound 5 which is the specific oxime compound of the said list | wrist.
The structures of Comparative Compound 1 and Comparative Compound 2 shown in the above list 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 specific compound 1 as a specific 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 cyclohexanone as a solvent A uniform composition (polymerizable composition 1) containing 16 g was prepared.
Using the obtained polymerizable composition 1 as a coating liquid, 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 (Grayscale film manufactured by Dainippon Screen Mfg. Co., Ltd.) is placed on this coating film, and the light of a 500 mW high-pressure mercury lamp manufactured by Ushio Electric is passed through a heat ray cut filter. After exposure for 30 seconds, development was performed by impregnation in toluene for 60 seconds.
When the number of steps completely cured and insolubilized corresponding to the step tablet was evaluated as sensitivity, the sensitivity was 7 steps.
In addition, a sensitivity step number shows that a sensitivity is so high that a number is large.

[Example 1-2 to Example 1-9 and Comparative Example 1-1 to Comparative Example 1-4]
In Example 1-1, 0.08 mmol of the specific compound used as the specific oxime compound was added to each compound shown in the above list (specific compound 2 to specific compound 9 and comparative compound 1 to comparative compound 4): The photopolymerizable composition 2 to the photopolymerizable composition 13 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 increased in the same manner as in Example 1-1. evaluated.
The evaluation results of Examples 1-1 to 1-9 and Comparative Examples 1-1 to 1-4 are shown in Table 1 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, C.I. I. 40 parts by mass of a 30/70 (mass ratio) mixture with CI Pigment Yellow 219, and 10 parts by mass of BYK2001 [Disperbyk: manufactured by Big Chemie (BYK), solid content concentration: 45.1% by mass] as a dispersant. 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 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, molar ratio: 80/10/10, Mw: 10,000)
-Polyfunctional monomer: 60 parts by mass of dipentaerythritol hexaacrylate-Specific oxime compound: 60 parts by mass of specific compound 1-Solvent: 1,000 parts by mass of propylene glycol monomethyl ether acetate-Surfactant (trade name: Tetranic 150R ¹ , BASF Corp.) 1 part by mass / γ-methacryloxypropyltriethoxysilane 5 parts by mass

[2. (Production of color filter)
2-1. Formation of colored photopolymerizable composition layer 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 for 10 minutes. In this state, vacuum drying and prebaking (100 ° C., 80 seconds) were performed to form a photopolymerizable composition coating film (colored 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 colored photopolymerizable composition layer was exposed in a pattern using a 2.5 kW ultra-high pressure mercury lamp. The entire surface of the colored photopolymerizable composition layer after exposure was covered with a 10% aqueous solution of an organic developer (trade name: CD, manufactured by Fuji Film Electronics Materials Co., Ltd.), and left still for 60 seconds.

2-3. Heat treatment Thereafter, pure water was sprayed onto the colored 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, pattern cross-sectional shape, and post-heat pattern cross-sectional shape were evaluated as follows. The evaluation results are summarized in Table 2.

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, using a 60% CD-2000 (Fuji Film Electronics Materials Co., Ltd.) developer, the exposed coating film was developed under conditions of 25 ° C. and 60 seconds. 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, color change with time of forced heating, 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

<Board adhesion>
The substrate adhesion was evaluated based on the following criteria by observing whether or not a pattern defect occurred. It is confirmed that it has hardened to the deep part of a composition film because this board | substrate adhesiveness is favorable.
-Evaluation criteria-
○: No pattern defect was observed. Δ: Pattern defect was hardly observed, but a part of the defect was observed.

<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

<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 rectangular, and next is forward taper. Reverse taper is not preferred.
<Post-heating pattern cross-sectional shape>
The cross-sectional shape of the pattern formed after post-baking in “2-3. Heat treatment” was observed and evaluated. The cross-sectional shape of the pattern is most preferably rectangular, and a forward taper is next preferred. Reverse taper is not preferred.

[Examples 2-2 to 2-17, Comparative Examples 2-1 to 2-3]
In the composition A-1 used for the preparation of the colored photopolymerizable composition A-1 in Example 2-1, 60 parts by mass of the specific compound 1 (specific oxime compound) is added to each compound and amount shown in Table 2 below. Instead, Examples 2-10 to 2-17 were all the same as Example 2-1 except that sensitizers and co-sensitizers were added in the types and amounts shown in Table 2 below. Colored photopolymerizable compositions A-2 to A-17 and CA-1 to CA-3 were prepared to obtain color filters. Furthermore, the same evaluation as in Example 2-1 was performed. The results are shown in Table 2.

In Table 2 and Tables 3 to 8 below, the numerical values 1 to 9 in the “specific compound” column in the “polymerization initiator” column indicate the specific compound 1 to the specific compound 9, and in the “comparative compound” column. Numerical values 1 to 3 indicate Comparative Compound 1 to Comparative Compound 3.
Sensitizer types A1 to A3, cosensitizer types F1 to F3, and LD-5 shown in Table 2 are the compounds shown below.

  From the results in Table 2, it can be seen that the colored photopolymerizable compositions of the Examples containing the specific oxime compounds (specific compound 1 to specific compound 9) are excellent in storage stability (time-lapse stability). In addition, these colored photopolymerizable compositions have high exposure sensitivity, excellent developability when used for forming a colored pattern of a color filter, the resulting colored pattern is not colored with heating, and the substrate It turns out that it is excellent in all of adhesiveness, pattern cross-sectional shape, and post-heating pattern cross-sectional shape.

[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 / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60/22/18) 40 % PGMEA solution]
・ Dipentaerythritol hexaacrylate (polymerizable compound)
12.20 parts by mass / polymerization inhibitor (p-methoxyphenol) 0.0061 parts by mass / fluorine surfactant 0.83 parts by mass (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
-Photopolymerization initiator 0.586 parts by mass [TAZ-107 (trihalomethyltriazine-based photopolymerization initiator),
(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]
A compound of the following composition B-1 was 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]
Specific compound 1 (specific oxime compound) 2.5 parts by mass Glycerol propoxylate 0.5 parts by mass [Number average molecular weight Mn: 1,500, 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 3 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 r. p. m. While being rotated, pure water was supplied from the upper part of the rotation center in the form of a shower through a spray nozzle, followed by rinsing treatment, and then spray drying.
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 3 below.

<Evaluation of developability, coloring over time, substrate adhesion, pattern cross-sectional shape, post-heat pattern cross-sectional shape>
Evaluation of developability, coloring over time, substrate adhesion, pattern cross-sectional shape, and post-heating pattern cross-sectional shape was performed based on the evaluation method and evaluation criteria performed for Example 2-1. The results are shown in Table 3 below.

[Examples 3-2 to 3-17, Comparative examples 3-1 to 3-4]
In Example 3-1, 2.5 parts by mass of the specific compound 1 (specific oxime compound) in the composition B-1 used for the preparation of the colored photopolymerizable composition B-1 and each compound shown in Table 3 below and Instead of the amount, Examples 3-10 to 3-17 were all except that sensitizers and co-sensitizers shown in Table 3 below were added in the types and amounts shown in Table 3 below. In the same manner as in Example 3-1, colored photopolymerizable compositions B-2 to B-17 and CB-1 to CB-4 were prepared to obtain color filters. Furthermore, the same evaluation as in Example 3-1 was performed. The results are shown in Table 3.

  Sensitizers A1 to A3, cosensitizers F1 to F3, and LD-5 shown in Table 3 are the compounds described above.

[Example 3-18]
A compound of the following composition C-1 was 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]
Specific compound 1 (specific oxime compound) 0.5 parts by mass Benzyl methacrylate / methacrylic acid copolymer 2.0 parts by mass (molar ratio = 70/30)

[Examples 3-19 to 3-34, Comparative examples 3-5 to 3-7]
In Example 3-18, 0.5 parts by mass of the specific compound 1 (specific oxime compound) in the composition C-1 used for the preparation of the colored photopolymerizable composition C-1 was used for each compound shown in Table 4 below. In addition to Example 3-27 to Example 3-34, the sensitizers and co-sensitizers shown in Table 4 below were added in the types and amounts shown in Table 4 below. In the same manner as in Example 3-18, colored photopolymerizable compositions C-2 to C-17 and CC-1 to CC-3 were prepared.

  Each colored photopolymerizable composition obtained was evaluated in the same manner as in Example 3-1. The results are shown in Table 4.

  Note that sensitizers A1 to A3, cosensitizers F1 to F3, and LD-5 shown in Table 4 are the compounds described above.

[Example 3-35]
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]
Specific compound 1 (specific oxime compound) 0.5 parts by mass Benzyl methacrylate / methacrylic acid copolymer 2.0 parts by mass (molar ratio = 70/30)

[Example 3-36 to Example 3-51, Comparative Example 3-8 to Comparative Example 3-10]
In Example 3-35, 0.5 parts by mass of the specific compound 1 (specific oxime compound) in the composition D-1 used for the preparation of the colored photopolymerizable composition D-1 was used for each compound shown in Table 5 below. In addition to Example 3-44 to Example 3-51, the sensitizers and co-sensitizers shown in Table 5 below were added in the types and amounts shown in Table 5 below. In the same manner as in Example 3-35, colored photopolymerizable compositions D-2 to D-17 and CD-1 to CD-3 were prepared.

  Each colored photopolymerizable composition obtained was evaluated in the same manner as in Example 3-1. The results are shown in Table 5.

  Note that sensitizers A1 to A3, cosensitizers F1 to F3, and LD-5 shown in Table 5 are the compounds described above.

From the results of Tables 3 to 5, the colored photopolymerizable composition of each Example containing the specific oxime compound (specific compound 1 to specific compound 9) is excellent in storage stability (temporal stability). I understand. In addition, these colored photopolymerizable compositions have high exposure sensitivity, excellent developability when used for forming a colored pattern of a color filter, the resulting colored pattern is not colored with heating, and the substrate It turns out that it is excellent in all of adhesiveness, pattern cross-sectional shape, and post-heating pattern cross-sectional shape.
Further, as is apparent from Table 5, it can be seen that even when the pigment content is high, the exposure sensitivity is excellent.

[Examples 4-1 to 4-38, Comparative examples 4-1 to 4-12]
(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 70,000 mPa · s.
Then, the following composition 2 was added to this dispersion, and it stirred for 3 hours using the homogenizer on the conditions of 3,000 rpm. 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 by mass- Propylene glycol monomethyl ether acetate 45% solution of benzyl methacrylate / methacrylic acid copolymer 22 parts by mass (BzMA / MAA = 70/30 Mw: 30,000 )
-Solsperse 5000 (manufactured by Zeneca) 1.2 parts by mass

(Composition 2)
-Benzyl methacrylate / methacrylic acid copolymer 45% propylene glycol monomethyl ether acetate solution 22 parts by mass (BzMA / MAA = 70/30 Mw: 30,000)
・ 200 parts by mass 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 75 nm Titanium black 13M-C 39 parts by mass (Mitsubishi Materials Corporation) (Pigment Black 35)
-Propylene glycol monomethyl ether acetate solution of benzyl (meth) acrylate / (meth) acrylic acid copolymer 8 parts by mass (BzMA / MAA = 70/30, Mw: 30,000, solid content 40% by mass)
・ Solsperse 5000 (manufactured by Zeneca) 1 part by mass

The following component 4 was added to the obtained dispersion, and the mixture was stirred for 3 hours using a homogenizer at 3,000 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 by mass of propylene glycol monomethyl ether acetate solution of benzyl (meth) acrylate / (meth) acrylic acid copolymer (BzMA / MAA = 70/30 Mw: 30,000, solid content 40% by mass)
・ 200 parts by mass of propylene glycol monomethyl ether acetate

<Preparation of Black Photopolymerizable Compositions E-1 to E-18 and CE-1 to CE-6>
The components of the following composition Ea were mixed with a stirrer to prepare black photopolymerizable compositions E-1 to E-18 and CE-1 to CE-6.

(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-The CB dispersion A, or 24 parts by mass of the TB dispersion A, 10 parts by mass of propylene glycol monomethyl ether acetate, 8 parts by mass of ethyl-3-ethoxypropionate, a compound described in Table 6 below: specific oxime compound or comparative compound
The amount and co-sensitizer described in Table 6 below: No addition of F3 or 0.1 parts by mass

<Preparation of Black Photopolymerizable Compositions E-19 to E-38 and CE-7 to CE-12>
The components of the following composition Eb were mixed with a stirrer to prepare black photopolymerizable compositions E-19 to E-38 and CE-7 to CE-12.

(Composition Eb)
-2.3 parts by mass of dipentaerythritol hexaacrylate-24 parts by mass of the CB dispersion A or TB dispersion A-10 parts by mass of propylene glycol monomethyl ether acetate-8 parts by mass of ethyl-3-ethoxypropionate- Compounds listed in Table 7: Specific oxime compounds or comparative compounds
Amount and co-sensitizer described in Table 7 below: No addition of F3 or 0.1 parts by mass

[Evaluation]
The following evaluations were performed using the black photopolymerizable compositions E-1 to E-38 and CE-1 to CE-12 obtained as described above. The results are summarized in Tables 6 and 7.

-Exposure sensitivity evaluation-
First, the exposure sensitivities of the black photopolymerizable compositions E-1 to E-38 and CE-1 to CE-12 obtained as described above were determined and evaluated by the following methods.

Using the black photopolymerizable compositions E-1 to E-38 and CE-1 to CE-12, the film thickness after heat treatment on 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 it was uniformly coated on a silicon wafer to obtain a 1.0 μm coating film.
Next, using an i-line stepper, FPA-3000iS + (manufactured by Canon Inc.), through a mask on which a 10 nm L & S (line and space) pattern is drawn, 100 to 5,100 mJ / cm ² Irradiation was performed while changing the exposure amount in a range of 100 mJ / cm ² .
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)-
Further, the storage stability (time stability) of the black photopolymerizable compositions E-1 to E-38 and CE-1 to CE-12 obtained as described above was evaluated by the following method.
That is, after storing the black photopolymerizable compositions E-1 to E-38 and CE-1 to CE-12 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-38 and CE-1 to CE-12 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 6 and 7, it can be seen that the black photopolymerizable composition of each Example containing the specific oxime compound is excellent in storage stability (time stability). 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.

[Example 5]
<Production of full-color color filter>
The black image pattern produced in Example 4-1 was used as a black matrix, and the colored photopolymerizable composition A-1 was used on the black matrix in the same manner as described in Example 3-1. A 1.6 × 1.6 μm green (G) colored pattern was formed.
Furthermore, only the pigment (30/70 [mass ratio] mixture of CI Pigment Green 36 and CI Pigment Yellow 219) is used for the colored photopolymerizable composition A-1 as a blue pigment (C Pigment Blue 15: 6 and CI Pigment Violet 23 30/70 [mass ratio] mixture) and red pigment (CI Pigment Red 254), respectively (B) A colored photopolymerizable composition of red (R) was prepared.
First, a 1.6 × 1.6 μm blue (B) and red (R) pattern was sequentially formed on the substrate in the same manner as that performed with the green (G) photopolymerizable composition A-1, and solid-state imaging was performed. A color filter for the device was produced.

  About the obtained full-color color filter, when the black image pattern and the colored pattern of each color of RGB, the cross-sectional shape and the substrate adhesion were evaluated in the same manner as in Example 2-1, each pattern was rectangular. In addition, it was found that there was no pattern defect and the substrate adhesion was excellent.

[Example 6]
<Production of solid-state image sensor>
When the full-color color filter obtained in Example 5 was incorporated into a solid-state imaging device, it was confirmed that the solid-state imaging device had high resolution and excellent color separation.

[Examples 7-1 to 7-15, Comparative examples 7-1 to 7-4]
<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 . The surface roughness measured was 0 to 45 μm (Ra indication). Subsequently, the aluminum plate was dipped in 30% H ₂ SO ₄ aqueous solution, desmutted at 55 ° C. for 2 minutes, and then placed at 33 ° C. in 20% H ₂ SO ₄ aqueous solution with a cathode disposed on the grained surface. When anodized for 50 seconds at a current density of 5 A / dm ² , the thickness was 2.7 g / m ² .
Thus, a support A-1 for a lithographic printing plate precursor was obtained.

<Formation of photosensitive layer>
On the obtained support A-1, 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 (M, N or O described in Table 8) 0.80 part by mass Binder polymer (B1, B2 or B3 described in Table 8) 0.90 part by mass Sensitizer (Table 8 A1, A2 or A3) No addition or 0.10 parts by mass. Compound described in Table 8 below: Specific oxime compound, comparative compound or LD-5
0.05 parts by mass / co-sensitizer (F2 or F3 listed in Table 8) No addition or 0.25 parts by mass / fluorine-based surfactant 0.02 parts by mass (Megafac F-177: Dainippon Ink Chemical Industry Co., Ltd.)
-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 printed with a solid image and a 1-99% halftone dot at a density of 175 lines / inch at 4,000 dpi using a violet LD (violet boxer manufactured by FFEI) with a wavelength of 405 nm and an exposure amount of 50 μJ / cm ^2. The image (in 1% increments) was 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, storage stability, and printing durability of the formed image area of the planographic printing plate precursors of Examples and Comparative Examples were evaluated by the following methods. The results are summarized in Table 8.

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. This printing durability supports the in-film curability.

3. Evaluation of forced aging (storage stability) All the same methods as those 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 without a standing at 60 ° C. for 4 days was taken, and the change in halftone dot (Δ%) with forced aging was measured. The smaller the absolute value of this number, the less the influence of forced aging, that is, the higher the storage stability.

  In Table 8, the details of M, N, O in the “addition polymerizable compound” column and B1, B2, and B3 in the “binder polymer” column are as follows. The following B3 is a copolymer of MDI / HMDI [molar ratio 80/20] and a copolymer of DMPA, PPG (m = 3) and TEG having the following structure [molar ratio 52/22/26] [Mixing ratio 50/50 (molar ratio)].

As is apparent from Table 8, the lithographic printing plate precursors of Examples 7-1 to 7-15 containing the specific oxime compound of the present invention in the photosensitive layer have high sensitivity, excellent storage stability, and printing durability. It can be seen that
On the other hand, the lithographic printing plate precursors of Comparative Examples 7-1 to 7-4 were inferior to the lithographic printing plate precursors of the examples in both sensitivity and printing durability.

Claims (13)

  (A) Oxime-based polymerization initiation having a condensed ring structure formed from a monocyclic structure selected from an aromatic ring and a heteroaromatic ring, and an aliphatic monocyclic structure comprising an oxime group directly bonded to a carbonyl group A polymerizable composition containing an agent and (B) a polymerizable compound. The polymerizable composition according to claim 1, wherein the (A) oxime polymerization initiator is a compound represented by the following general formula (1).

In the general formula (1), Ar represents a monocyclic structure selected from an aromatic ring and a heteroaromatic ring. A represents a single bond or a divalent linking group. X represents —CH ₂ —, —O—, —S— or —NR—, and R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ^1A and R ^1B each independently represent a hydrogen atom, an alkyl group or an aryl group. R ³ represents an acyl group or a sulfonyl group. The polymerizable composition according to claim 1 or 2, wherein the (A) oxime polymerization initiator is a compound represented by the following general formula (2).

In the general formula (2), A represents a single bond or an alkylene group having 1 to 2 carbon atoms. X represents —CH ₂ —, —O—, —S— or —NR—, and R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ^1A and R ^1B each independently represent a hydrogen atom, an alkyl group or an aryl group. R ³ represents an acyl group or a sulfonyl group.
R ² , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, hydroxyl group, alkoxy group, aryloxy group, amino group, mercapto group Represents an alkylthio group or an arylthio group. The polymerizable composition according to claim 1 or 2, wherein the (A) oxime polymerization initiator is a compound represented by the following general formula (3).

In the general formula (3), R ^1A and R ^1B each independently represent a hydrogen atom, an alkyl group, or an aryl group. R ³ represents an acyl group or a sulfonyl group.
R ² , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, hydroxyl group, alkoxy group, aryloxy group, amino group, mercapto group Represents an alkylthio group or an arylthio group.   Furthermore, (C) The polymeric composition of any one of Claims 1-4 containing a coloring agent.   The polymerizable composition according to claim 5, wherein the (C) colorant is a pigment and further contains (D) a pigment dispersant.   The polymerizable composition according to claim 5 or 6, wherein the (C) colorant is a black colorant.   The polymerizable composition according to any one of claims 5 to 7, which is used for forming a colored region of a color filter.   A color filter having a colored region formed using the polymerizable composition according to claim 8 on a support. Applying a polymerizable composition according to claim 8 on a support to form a polymerizable composition layer;
Exposing the polymerizable composition layer in a pattern; and
Developing the polymerizable 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 9.   A lithographic printing plate precursor having a photosensitive layer containing the polymerizable composition according to any one of claims 1 to 5 on a support. A compound represented by the following general formula (3).

In the general formula (3), R ^1A and R ^1B each independently represent a hydrogen atom, an alkyl group, or an aryl group. R ³ represents an acyl group or a sulfonyl group.
R ² , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, hydroxyl group, alkoxy group, aryloxy group, amino group, mercapto group , An alkylthio group, or an arylthio group.