JP2009109921A - Photopolymerizable composition for color filer, color filter and method for producing same, and solid-state imaging device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photopolymerizable composition for color filers which, even with a high colorant concentration, is capable of curing with high sensitivity, has good pattern forming property and is excellent in removability of an uncured part, a color filter which has a colored pattern of a good shape and suppresses occurrence of residues in a region where the colored pattern is not formed, a production method by which the color filter can be produced with high productivity, and a solid-state imaging device including the color filter. <P>SOLUTION: The photopolymerizable composition for color filers comprises (A) a compound represented by general formula (I), (B) a polyfunctional photopolymerizable compound having one or more acidic functional groups and/or one or more alkyleneoxy chains, and (C) a colorant, wherein R and B each independently represent a monovalent organic group; X represents a monovalent substituent; Y<SP>1</SP>and Y<SP>2</SP>each independently represent a monovalent substituent; and n<SB>1</SB>represents an integer of 0-4. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photopolymerizable composition for a color filter, a color filter, a method for producing the same, and a solid-state imaging device.

  As a method for producing a color filter used for a liquid crystal display element or a solid-state imaging element, a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method are known.

  Among these, the pigment dispersion method is a method for producing a color filter by a photolithographic method using a colored photopolymerizable composition in which a pigment is dispersed in various photopolymerizable compositions. It has the advantage of being stable to heat and the like. In addition, the pigment dispersion method is widely used as a method suitable for producing a color filter for a large screen and a high-definition color display because it is patterned by a photolithographic method with high positional accuracy.

  When producing a color filter by the pigment dispersion method, a photopolymerizable composition is applied and dried on a glass substrate with a spin coater or roll coater to form a coating film, and the coating film is subjected to pattern exposure and development. A color filter can be obtained by forming colored pixels and repeating this operation for each color. Regarding color filter formation using a pigment dispersion method, there is one using a photopolymerizable colored resin composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin (see, for example, Patent Document 1). ).

On the other hand, in recent years, it has been desired that the color filters for solid-state imaging devices have higher definition and thinner thickness. For example, as a technique for forming a thin film in which spectral characteristics are maintained, a technique for increasing the colorant content in the total solid content of the photopolymerizable composition and improving the pattern formability with a resin is disclosed (for example, And Patent Documents 2 and 3).

  However, in the composition as described in Patent Documents 2 and 3, if the content of the colorant is further improved, the sensitivity is remarkably lowered, and the problem that the pattern peels off in the low exposure amount region occurs. Furthermore, since the coloring material (coloring agent) is contained at a high concentration, there is a problem that a residue is easily generated between pixels (pattern non-formation region). In particular, in color filters for solid-state imaging devices, there is a strong demand for high color density and thinning of color filters in order to improve image quality due to high light-condensing properties and high color separation of solid-state imaging devices such as CCDs. Improvements have been desired for low sensitivity and generation of residues as described above.

  In addition, in order to obtain a high color density in the color filter, when a large amount of colorant is added to the photopolymerizable composition used for forming the pixel pattern, for example, the shape of a fine pixel pattern of 2.5 μm or less is faithfully reproduced. Therefore, the sensitivity is insufficient, and there is a tendency that pattern loss frequently occurs as a whole.

As described above, regarding the photopolymerizable composition for a color filter, it is necessary to obtain a good pattern forming property even when the colorant is contained at a high concentration, and therefore it is desired that the curing sensitivity is high. This is the current situation. From the viewpoint of improving the curing sensitivity, an embodiment in which the addition amount of the polymerization initiator contained in the photopolymerizable composition is increased. However, when the addition amount of the polymerization initiator is increased, the removability of the uncured part is lowered, and particularly when a Bayer pattern having a pattern size of 1.5 μm or less is formed, a remarkable residue is left in the non-formation region of the colored pattern. There was a problem that occurred. In order to improve such a problem of residue generation, for example, there is an embodiment in which a photopolymerizable compound having a hydrophilic group is applied. However, in this case, there is a problem that sensitivity is lowered. .
JP-A-2-199403 JP 2006-276878 A Japanese Patent No. 3823579

This invention is made | formed in view of the said situation, and makes it a subject to achieve the following objectives.
That is, the object of the present invention is for a color filter that cures with high sensitivity, has a good pattern forming property, and is excellent in removal of an uncured portion even when it contains a colorant at a high concentration. The object is to provide a photopolymerizable composition.
Another object of the present invention is to provide a color filter having a colored pattern of a good shape, in which residues in the non-formation region of the colored pattern are suppressed, a production method capable of producing the color filter with high productivity, and An object of the present invention is to provide a solid-state imaging device including the color filter.

  As a result of intensive studies, the present inventors have developed a photopolymerizability containing a compound having a specific structure with high absorption efficiency for light having a wavelength of 365 nm or 405 nm, and a polyfunctional photopolymerizable compound having a specific structure. The present inventors have found that the above problems can be solved by the composition, and have completed the present invention. That is, the means for solving the problems are as follows.

  <1> (A) a compound represented by the following general formula (I), (B) a polyfunctional photopolymerizable compound having one or more acidic functional groups and / or one or more alkyleneoxy chains, and (C ) A photopolymerizable composition for a color filter, comprising a colorant.

In general formula (I), R and B each independently represent a monovalent organic group, X represents a monovalent substituent, Y ¹ and Y ² each independently represent a monovalent substituent, and n ₁ represents an integer of 0 to 4.

  <2> The photopolymerizability for a color filter according to <1>, wherein the compound represented by (A) the general formula (I) is a compound represented by the following general formula (II): Composition.

In general formula (II), R and B each independently represent a monovalent organic group, Z represents a monovalent substituent, and n ₂ represents an integer of 0 to 5.

  <3> The polyfunctional photopolymerizable compound (B) having one or more acidic functional groups and / or one or more alkyleneoxy chains is represented by the following general formula (1), general formula (2), or general formula: (3) The photopolymerizable composition for color filters as described in <1> or <2> above, which is a compound represented by (3).

In General Formula (1), R ¹ , T ¹ , and X ¹ each independently represent any of the groups shown below as R ¹ , T ¹ , or X ¹ . n represents an integer of 0 to 14.

In General Formula (2), Z ¹ and G ¹ each independently represent any of the groups shown below as Z ¹ or G ¹ . W ¹ is synonymous with the group represented by R ¹ or X in the general formula (1), and 3 or more of 6 W ¹ represent R ¹ . p represents an integer of 0 to 14.

In general formula (3), each R ² independently represents a substituent containing an ethylenic double bond or a substituent containing a hydroxy group, and at least one of the plurality of R ² is alkylene in the structure. Has an oxide chain.

  <4> Content of said (C) coloring agent is 50 mass% or more with respect to the total solid of a photopolymerizable composition, Any one of said <1>-<3> characterized by the above-mentioned. Item 4. A photopolymerizable composition for a color filter according to the item.

  <5> A color filter having a coloring pattern using the photopolymerizable composition for a color filter according to any one of <1> to <4>.

<6> Forming a photopolymerizable composition layer by applying the photopolymerizable composition for a color filter according to any one of <1> to <4> above on a support;
Exposing the photopolymerizable composition layer through a mask;
Developing the photopolymerizable composition layer after exposure to form a colored pattern; and
A method for producing a color filter, comprising:

  <7> A solid-state imaging device comprising the color filter according to <5>.

According to the present invention, even when the colorant is contained at a high concentration, the photopolymerizable composition is cured with high sensitivity, has a good pattern forming property, and is excellent in removal of an uncured part. Can be provided.
In addition, according to the present invention, a color filter having a colored pattern with a good shape, in which a residue in a non-formation region of the colored pattern is suppressed, a manufacturing method capable of manufacturing the color filter with high productivity, and A solid-state imaging device including the color filter can be provided.

[Photopolymerizable composition for color filter]
The photopolymerizable composition for color filters of the present invention (hereinafter sometimes simply referred to as “photopolymerizable composition”) is (A) a compound represented by the general formula (I), (B) 1 A photopolymerizable composition comprising a polyfunctional photopolymerizable compound having one or more acidic functional groups and / or one or more alkyleneoxy chains, and (C) a colorant.

<(A) Compound represented by Formula (I)>
The photopolymerizable composition of the present invention contains a compound represented by the following general formula (I) (hereinafter, appropriately referred to as “specific oxime compound”). The specific oxime compound is a compound that can function as a photopolymerization initiator.

In general formula (I), R and B each independently represent a monovalent organic group, X represents a monovalent substituent, Y ¹ and Y ² each independently represent a monovalent substituent, and n ₁ represents an integer of 0 to 4.

If n ₁ is an integer of 2 to 4, X existing in plural numbers may be the same or different.

The compound represented by formula (I) (specific oxime compound) will be described in detail.
Examples of the monovalent organic group represented by R include an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkenyl group that may have a substituent, and a substituent. An alkynyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent. A good arylsulfonyl group, an optionally substituted acyl group, an optionally substituted alkoxycarbonyl group, an optionally substituted aryloxycarbonyl group, and an optionally substituted phosphinoyl Group, a heterocyclic group which may have a substituent, an alkylthiocarbonyl group which may have a substituent, an arylthiocarbonyl group which may have a substituent, a dialkylaminocarbonyl which may have a substituent , Good dialkylaminothiocarbonyl group, or the like may have a substituent.

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

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, such as a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, and a 9-phenanthryl. Group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl, mesityl, pentarenyl, binaphthalenyl, tarnaphthalenyl, quarternaphthalenyl, heptalenyl, biphenylenyl, indacenyl, fluoranthenyl, acenaphthylenyl, aceanthrylenyl Group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, taran Rasenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

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

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

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

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

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

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

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

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

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

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

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

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

  As the arylthiocarbonyl group which may have a substituent, for example, 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, 4 -Dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenyl Thiocarbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenyl Thiocarbonyl group, and 4-methoxyphenyl thiocarbonyl group.

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

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

  Among these, from the viewpoint of increasing sensitivity, an acyl group is more preferable as the monovalent organic group represented by R, and specifically, an acetyl group, an ethyloyl group, a propioyl group, a benzoyl group, and a toluyl group are preferable.

  As specific examples of the monovalent organic group represented by R, those shown below are preferable from the viewpoint of increasing sensitivity.

The monovalent organic group represented by B includes a phenyl group (however, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, —OR ⁸ , —SR ⁹ or —N (R ¹⁰ ) (R ¹¹ ), An alkyl group having 1 to 20 carbon atoms (provided that the alkyl group has 2 to 20 carbon atoms, one or more carbon atoms constituting the main chain may be substituted with one or more carbon atoms). May have an oxygen atom or an S atom, or may be substituted with one or more hydroxy groups.), An alkenyl group having 1 to 20 carbon atoms (provided that the alkyl group has 2 to 20 carbon atoms) , May have one or more oxygen atoms or S atoms between carbon atoms constituting the main chain, or may be substituted with one or more hydroxy groups.), An alkynyl group having 1 to 20 carbon atoms (However, when the alkyl group has 2 to 20 carbon atoms, the main chain May have one or more oxygen atoms or S atoms between the carbon atoms constituting it, or may be substituted with one or more hydroxy groups), a cycloalkyl group having 5 to 8 carbon atoms, carbon Substituted with one or more of an alkanoyl group and a benzoyl group having 2 to 20 carbon atoms (wherein the alkyl group has 1 to 6 carbon atoms, a phenyl group, -OR ⁸ , -SR ⁹ or -N (R ¹⁰ ) (R ¹¹ )) Or an alkoxycarbonyl group having 2 to 12 carbon atoms (provided that when the alkoxyl group has 2 to 11 carbon atoms, the alkoxyl group has one or more oxygen atoms between the carbon atoms constituting the main chain). Or may be substituted with one or more hydroxy groups), a phenoxycarbonyl group (however, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, —OR ⁸ or —N ( R ¹⁰ ) (It may be substituted with one or more of (R ¹¹ ).), A cyano group, a nitro group, —CON (R ¹⁰ ) (R ¹¹ ), a haloalkyl group having 1 to 4 carbon atoms, —S (O) m— R ^{12 (where, R 12} represents an alkyl group having 1 to 6 carbon atoms, m is an integer of 0~2.), - S (O ) m-R 13 ( ^{where, R 13} is 6 carbon atoms 12 is an aryl group having 12 carbon atoms and may be substituted with an alkyl group having 1 to 12 carbon atoms, and m is an integer of 0-2.), An alkoxysulfonyl group having 1 to 6 carbon atoms, and a carbon atom having 6 to 10 carbon atoms. Examples include an aryloxysulfonyl group or a diphenylphosphinoyl group.

R ⁸ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a substituted alkyl group having 2 to 6 carbon atoms (provided that the substituent is a hydroxy group, a mercapto group, a cyano group, or an alkyl group having 1 to 4 carbon atoms). An alkoxyl group, an alkenyloxy group having 3 to 6 carbon atoms, a 2-cyanoethoxy group, a 2- (alkoxycarbonyl) ethoxy group having 4 to 7 carbon atoms, an alkylcarbonyloxy group having 2 to 5 carbon atoms, a phenylcarbonyloxy group, It consists of one or more of a carboxyl group or a C2-C5 alkoxycarbonyl group. }, An alkyl group having 2 to 6 carbon atoms having one or more oxygen atoms between carbon atoms constituting the main chain, an alkanoyl group having 2 to 8 carbon atoms, — (CH ₂ CH ₂ O) nH (where n Is an integer of 1 to 20), an alkenyl group having 3 to 12 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms, a cyclohexyl group, a phenyl group (however, a halogen atom, an alkyl group having 1 to 12 carbon atoms, or a carbon atom) Or a phenylalkyl group having 7 to 9 carbon atoms, —Si (R ¹⁴ ) r (R ¹⁵ ) ₃ —r (wherein R ¹⁴ has 1 to 1 carbon atoms) 8 represents an alkyl group, R ¹⁵ represents a phenyl group, and r represents an integer of 1 to 3.

R ⁹ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, a cyclohexyl group, a substituted alkyl group having 2 to 6 carbon atoms {provided that the substituent is a hydroxy group, Mercapto group, cyano group, alkoxy group having 1 to 4 carbon atoms, alkenyloxy group having 3 to 6 carbon atoms, 2-cyanoethoxy group, 2- (alkoxycarbonyl) ethoxy group having 4 to 7 carbon atoms, 2 to 2 carbon atoms It consists of one or more of 5 alkylcarbonyloxy groups, phenylcarbonyloxy groups, carboxyl groups or C2-C5 alkoxycarbonyl groups. }, An alkyl group having 2 to 12 carbon atoms having at least one oxygen atom or sulfur atom between carbon atoms constituting the main chain, a phenyl group (however, a halogen atom, an alkyl group having 1 to 12 carbon atoms or a carbon number) 1 to 4 alkoxyl groups may be substituted.), A phenylalkyl group having 7 to 9 carbon atoms.

The monovalent substituent represented by X, Y ¹ , or Y ² may have an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. An alkenyl group, an alkynyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, Arylsulfonyl group which may have a substituent, acyl group which may have a substituent, alkoxycarbonyl group which may have a substituent, aryloxycarbonyl group which may have a substituent, substituent A phosphinoyl group that may have a substituent, a heterocyclic group that may have a substituent, an alkylthioxy group that may have a substituent, an arylthioxy group that may have a substituent, and a substituent. An alkyloxy group, Aryloxy group which may have a group, alkylthiocarbonyl group which may have a substituent, arylthiocarbonyl group which may have a substituent, dialkylaminocarbonyl group which may have a substituent, substituted A dialkylaminothiocarbonyl group which may have a group, a carboxylic acid group, a sulfonic acid group, a cyano group, a halogen atom, an amino group which may have a substituent, a substituent formed by combining these, and the like Can be mentioned.

Among them, the monovalent substituent represented by X, Y ¹ , or Y ² is a hydrogen atom, an alkoxycarbonyl group, a cyano group, or a phenyl group from the viewpoint of improving sensitivity and stability over time of the composition. Is preferred.

^Two of the monovalent substituents represented by X, Y ¹ and Y ² may be bonded to each other to form a ring structure.

n ₁ represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1.

Although the example of the following partial structure (A) which is a partial structure connected with carbonyl carbon in General formula (I) is given to the following, it is not limited to these. The details of X, Y ¹ , Y ² , and n _{1 in} the partial structure (A) below are as described in the description of the general formula (I).

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

In general formula (II), R and B each independently represent a monovalent organic group, Z represents a monovalent substituent, and n ₂ represents an integer of 0 to 5.

B in the general formula (II) has the same meaning as B in the general formula (I), and the preferred range is also the same.
R in the general formula (II) has the same meaning as R in the general formula (I), and the preferred range is also the same.

N ₂ in the general formula (II) represents an integer of 0 to 5, an integer of 0 to 3 is preferable, and 0 or 1 is preferable. When n2 represents an integer of ₂ to 5, Z may be the same substituent or different substituents.

  Examples of the monovalent substituent represented by Z include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; phenoxy group, p -Aryloxy group such as tolyloxy group; alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group; acyloxy group such as acetoxy group, propionyloxy group, benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, Acyl groups such as acryloyl group, methacryloyl group and methoxalyl group; alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; methylamino group, cyclo Alkylamino groups such as xylamino group; dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group, piperidino group and julolidine group; arylamino groups such as phenylamino group and p-tolylamino group; methyl group, ethyl group, tert -Alkyl groups such as butyl group and dodecyl group; aryl groups such as 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, dimethylsulfoniu Mill group, triphenyl None Le phosphonate Niu mill group, a cyano group, and the like.

The following partial structure (B), which is a partial structure linked to the carbonyl carbon in the general formula (II), is a more preferred embodiment of the partial structure (A) described above, and as an example of the partial structure (A), Among the structures listed above, examples include structures included in the range of the partial structure (B). That is, examples of the partial structure (B) below include the following structures among the structures listed above as examples of the partial structure (A), but are not limited thereto.
The details of Z and n ₂ in the partial structure (B) below are as described above in the description of the general formula (II).

  Although the specific example of a specific oxime compound is shown below, it is not limited to these.

  Although a specific oxime compound can be synthesize | combined by the method shown below, for example, it is not limited to this method.

  More specifically, the specific oxime compound can be synthesized, for example, by the method shown below.

-Synthesis example of specific oxime compounds-
Ethyl carbazole is dissolved in chlorobenzene, and after cooling to 0 ° C., aluminum chloride is added. Subsequently, o-tolyl chloride is added dropwise over 40 minutes, and the mixture is warmed to room temperature and stirred for 3 hours. Next, after cooling to 0 ° C., aluminum chloride is added. 4-Chlorobutyryl chloride is added dropwise over 40 minutes, and the mixture is warmed to room temperature and stirred for 3 hours. A mixed solution of 35 wt% hydrochloric acid aqueous solution and distilled water is cooled to 0 ° C., and the reaction solution is added dropwise. The precipitated solid is filtered with suction, washed with distilled water and methanol, and recrystallized with acetonitrile to obtain Compound A having the following structure.

  Next, compound A is dissolved in THF, 4-chlorobenzenethiol and sodium iodide are added, sodium hydroxide is subsequently added to the reaction solution, and the mixture is refluxed for 2 hours. Further, after cooling to 0 ° C., SM-28 is added dropwise over 20 minutes, the temperature is raised to room temperature, and the mixture is stirred for 2 hours. Next, after cooling to 0 ° C., isopentyl nitrite is added dropwise over 20 minutes, the temperature is raised to room temperature, and the mixture is stirred for 3 hours. The reaction solution is diluted with acetone and added dropwise to a 0.1N aqueous hydrochloric acid solution cooled to 0 ° C. The precipitated solid is filtered with suction, washed with distilled water, and recrystallized with acetonitrile to obtain Compound B having the following structure.

  Compound B is dissolved in N-methylpyrrolidone and triethylamine is added. Next, after cooling to 0 ° C., acetyl chloride is added dropwise over 20 minutes, and then the temperature is raised to room temperature and stirred for 2 hours. The reaction solution is added dropwise to distilled water cooled to 0 ° C., and the precipitated solid is filtered with suction, washed with isopropyl alcohol cooled to 0 ° C., and dried to obtain the specific oxime compound (A).

  In the above synthesis examples of the specific oxime compound, the same operation is performed except that ethylcarbazole, o-tolyl chloride, and 4-chlorobutyryl chloride are changed to have a desired specific photopolymerization initiator structure. Thus, the specific oxime compound of another embodiment can be obtained. Moreover, the structure of the obtained specific oxime compound can be identified by NMR.

  The specific oxime compound has a maximum absorption wavelength in a region of 350 nm to 500 nm, and is particularly a compound having high absorption efficiency with respect to light having wavelengths of 365 nm and 455 nm.

  A specific oxime compound may be used individually by 1 type, and may use 2 or more types together.

  The content of the specific oxime compound is preferably 0.1% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 25% by mass or less in the total solid content of the photopolymerizable composition, and 2% by mass. More preferred is 20% by mass or less.

-Other polymerization initiators-
The photopolymerizable composition may be used in combination with a known photopolymerization initiator together with the specific oxime compound as long as the effects of the present invention are not impaired. The photopolymerization initiator that can be used in combination is a compound that can be decomposed by light to initiate and accelerate the polymerization of the polymerizable compound, and preferably has an 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.

  When the photopolymerizable composition contains another polymerization initiator, the content ratio of the specific oxime compound and the other polymerization initiator (specific oxime compound: other polymerization initiator) is 90:10 to 10 by mass ratio. 20:80 is preferable, 85: 15-30: 70 is more preferable, and 80: 20-40: 60 is still more preferable.

<(B) Polyfunctional photopolymerizable compound having one or more acidic functional groups and / or one or more alkyleneoxy chains>
The photopolymerizable composition of the present invention comprises (B) a polyfunctional photopolymerizable compound having one or more acidic functional groups and / or one or more alkyleneoxy chains (hereinafter referred to as “specific photopolymerizable compound” as appropriate). Containing).

  Here, the “polyfunctional photopolymerizable compound” means a compound having two or more photopolymerizable functional groups.

  As the form of the specific photopolymerizable compound, (B-1) a polyfunctional photopolymerizable compound having one or more acidic functional groups and having no alkyleneoxy chain (hereinafter also referred to as “AO chain”), ( B-2) a polyfunctional photopolymerizable compound having one or more AO chains and no acidic functional group, (B-3) a polyfunctional compound having one or more acidic functional groups and one or more AO chains There are three forms of functional photopolymerizable compounds.

  When two or more specific photopolymerizable compounds are contained in the photopolymerizable composition of the present invention, from the group including compounds belonging to one of the three forms (B-1) to (B-3). Two or more compounds may be selected, or two or more compounds may be selected from the group including compounds belonging to different forms.

  As the specific photopolymerizable compound, it is preferable to use a compound having a relatively small molecular size. In particular, it is preferable to use a compound having a polystyrene equivalent weight average molecular weight of less than 3,000.

  When the specific photopolymerizable compound having an acidic functional group is contained in the photopolymerizable composition, the crosslink density is increased by the photopolymerizable functional group of the compound, and the alkali solubility is increased by the acidic functional group of the compound. Therefore, in the photopolymerizable composition, a specific photopolymerizable compound having an acidic functional group is added even if the amount of a component that does not have curing reactivity and is not alkali-soluble, such as a colorant or a photopolymerization initiator, is increased. By doing so, the crosslink density and alkali solubility are increased, so that excellent polymerizability and alkali developability can be obtained.

  The specific photopolymerizable compound having an acidic functional group is preferably a compound that can be dissolved or dispersed in an alkaline developer. Examples of the acidic functional group possessed by the specific photopolymerizable compound include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. From the viewpoint of solubility in an alkali developer and handling of the composition, the carboxyl group is preferable.

  Further, when a specific photopolymerizable compound having an alkyleneoxy chain is contained in the photopolymerizable composition, the photopolymerizable functional group of the compound increases the crosslink density, and the hydrophilicity is improved by the alkyleneoxy chain of the compound. Thus, the solubility in a water-based alkaline developer as a developer is also improved. Therefore, the photopolymerizable composition contains a specific photopolymerizable compound having an alkyleneoxy chain even if the amount of a component that does not have curing reactivity and is not alkali-soluble, such as a colorant or a photopolymerization initiator, is increased. By doing so, the crosslink density and alkali solubility are increased, so that excellent polymerizability and alkali developability can be obtained.

The reaction mode of the photopolymerizable functional group possessed by the specific photopolymerizable compound is not limited, and may be any of photo radical reaction, photo cation reaction, and photo anion reaction.
The photopolymerizable functional group is preferably a photoradical reactive group such as photoradical polymerization or photoradical dimerization, and particularly a group containing an ethylenically unsaturated bond such as a (meth) acryloyl group. Are preferable, more preferably an acryloyl group and a methacryloyl group, and still more preferably an acryloyl group.

In order to increase the crosslinking density when the photopolymerizable composition is cured, the number of photopolymerizable functional groups of the specific photopolymerizable compound is preferably large.
The number of photopolymerizable functional groups possessed by the specific photopolymerizable compound having an AO chain is preferably 3 or more, more preferably 3 to 30, and still more preferably 3 to 15 from the viewpoint of crosslinking density.
The number of photopolymerizable functional groups possessed by the specific photopolymerizable compound having an acidic functional group is preferably 3 or more from the viewpoint of crosslinking density.

  The specific photopolymerizable compound having an acidic functional group includes (1) a carboxyl group introduced by modifying a monomer or oligomer having a hydroxy group and three or more photopolymerizable functional groups with a dibasic acid anhydride. Alternatively, (2) a compound in which a sulfonic acid group is introduced by modifying an aromatic compound having three or more photopolymerizable functional groups with concentrated sulfuric acid or fuming sulfuric acid can be used. Moreover, you may use the oligomer which contains the monomer which is the specific photopolymerizable compound itself as a repeating unit as a specific photopolymerizable compound.

The specific photopolymerizable compound in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (1) or (2).
In general formula (1) and general formula (2), when T or G represents an alkyleneoxy chain, the carbon atom side end is bonded to R, X, and W.

In General Formula (1), R ¹ , T ¹ , and X ¹ each independently represent any of the groups shown below as R ¹ , T ¹ , or X ¹ . n represents an integer of 0 to 14.

In General Formula (2), Z ¹ and G ¹ each independently represent any of the groups shown below as Z ¹ or G ¹ . W ¹ is synonymous with the group represented by R ¹ or X ¹ in the general formula (1), and 3 or more of 6 W ¹ represent R ¹ . p represents an integer of 0 to 14.

Among the compounds represented by the general formula (1) or the general formula (2), a pentaerythritol derivative and / or a dipentaerythritol derivative is more preferable.
Specifically, exemplary compounds (A-1) to (A-12) shown below are preferable, and exemplary compounds (A-1), (A-2), (A-3), and (A-5) are particularly preferable. And (A-7) are most preferred.

  The specific photopolymerizable compound in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).

In the general formulas (i) and (ii), each E ¹ independently represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) —. , Y each independently represents an integer of 0 to 10, and X ² each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.

In Formula (i), the total of acryloyl group and methacryloyl group represented by X ² is a three or four.

In general formula (ii), there may a total of acryloyl group and methacryloyl group represented by X ² is 5 or 6.

In general formula (i), m represents the integer of 0-10 each independently, and the sum total of each m is an integer of 0-40. However, if the sum of each m is 0, any one of X ² is a carboxyl group. As m, the integer of 0-6 is preferable and the integer of 0-4 is more preferable. Moreover, the integer of 2-40 is preferable, as for the sum total of each m, the integer of 2-16 is more preferable, and the integer of 4-8 is still more preferable.

In general formula (ii), n represents the integer of 0-10 each independently, and the sum total of each n is an integer of 0-60. However, if the sum of the n is 0, any one of X ² is a carboxyl group. As n, the integer of 0-6 is preferable and the integer of 0-4 is more preferable. Moreover, the integer of 3-60 is preferable, the total of each n is more preferable, the integer of 3-24 is more preferable, and the integer of 6-12 is still more preferable.

In general formula (i) or formula (ii) in the _{- ((CH 2) y CH} 2 O) - or _{- ((CH 2) y CH} (CH 3) O) - , the oxygen atom side ends There form that binds to X ² are preferred.

The compound represented by general formula (i) or (ii) may be used individually by 1 type, and may be used together 2 or more types. In particular, in the general formula (ii), a form in which all six X ² are acryloyl groups is preferable.

  Moreover, when using the compound represented by general formula (i) or (ii), as a total content in the specific photopolymerizable compound of this compound, 20 mass% or more is preferable, and 50 mass% or more is more preferable. .

  The compound represented by the general formula (i) or (ii) has a ring-opening skeleton by a ring-opening addition reaction of pentaerythritol or dipentaerythritol with ethylene oxide or propylene oxide, which is a conventionally known process. It can be synthesized from the step of bonding and the step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with the terminal hydroxy group of the ring-opened skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).

  Among the compounds represented by general formula (i) and general formula (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.

  Specific examples include the following exemplary compounds (a) to (f), and among them, exemplary compounds (a), (b), (e), and (f) are preferable.

  As a more specific example of such a compound, exemplary compound (13) (more specific embodiment of the exemplary compound (b)) is shown below, but is not limited thereto.

  As a commercial item of the specific photopolymerizable compound represented by the general formula (i) or the general formula (ii), for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples include DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains.

  Moreover, as a commercial item of the specific photopolymerizable compound represented by General formula (1) or General formula (2), TO-756 which is carboxyl group containing trifunctional acrylate made from Toagosei Co., Ltd., and carboxyl, for example And TO-1382, which is a group-containing pentafunctional acrylate.

  As the specific photopolymerizable compound in the present invention, a compound represented by the following general formula (3) is also preferable.

In general formula (3), each R ² independently represents a substituent containing an ethylenic double bond or a substituent containing a hydroxy group, and at least one of the plurality of R ² is alkylene in the structure. Has an oxide chain.
A plurality of R ² present in one molecule may be the same or different.

From the viewpoint of the crosslinking density when the photopolymerizable composition of the present invention is cured, the number of substituents containing an ethylenic double bond represented by R ² in the sex compound represented by the general formula (3) Is preferably 3 or more, more preferably 4 to 10, and still more preferably 5 to 6.

  Among the compounds represented by the general formula (3), from the viewpoint of improving developability, a compound represented by the following general formula (4) is preferable, and is a compound represented by the following general formula (5). Most preferably it is.

In the general formula (4), each R ³ independently represents a substituent containing an ethylenic double bond, and at least one of the plurality of R ³ has an alkylene oxide chain in the structure thereof. A plurality of R ³ present in one molecule may be the same or different.

In General Formula (5), each R ⁴ independently represents a substituent containing an ethylenic double bond.
A plurality of R ⁴ present in one molecule may be the same or different.

Hereinafter, specific examples of the compound represented by the general formula (3) include exemplified compounds (B-1) to (B-32), but are not limited thereto.
In the following exemplary compounds, the partial structure having an alkylene oxide in parentheses represents an alkylene oxide chain composed of 2 to 40 repeating units.

  The content of the specific photopolymerizable compound is preferably 50% by mass or more and 5% by mass or less, and 45% by mass or more in the total solid content of the photopolymerizable composition from the viewpoint of balance between curing sensitivity and residue generation. 10 mass% or less is more preferable, and 40 mass% or more and 15 mass% or less are still more preferable.

-Other photopolymerizable compounds-
The photopolymerizable composition of the present invention may contain a photopolymerizable compound other than the specific photopolymerizable compound as long as the effects of the present invention are not impaired.

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

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

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

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

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

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

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

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

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

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

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

<(C) Colorant>
The photopolymerizable composition contains (C) a colorant. By containing a colorant, a colored photopolymerizable composition having a desired color can be obtained.
In addition, since the photopolymerizable composition contains a specific oxime compound having excellent sensitivity to a 365 nm or 406 nm light source which is a short wavelength light source, it has high sensitivity even when it contains a colorant at a high concentration. Can be cured.

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

  Hereinafter, the colorant applicable to the photopolymerizable composition 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 property, the average particle diameter of the pigment is 0.01 μm or more. 0.1 μm or less is preferable, and 0.01 μm or more and 0.05 μm or less is more preferable.

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

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

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

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

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

  These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment , Etc. can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Mixing with CI Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. If it is 100: 4 or less, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. When the ratio is 100: 51 or more, the dominant wavelength is shorter than the short wavelength, and the deviation from the NTSC target hue may be large. 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. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. When the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 nm to 450 nm, and the color purity may not be improved. When the ratio exceeds 100: 150, the dominant wavelength becomes longer and the deviation from the NTSC target hue may increase. 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. If it is 100: 61 or more, the dispersion stability may decrease.

  In the photopolymerizable composition, when the colorant is a dye, a colored composition in a state of being uniformly dissolved in the composition can be obtained.

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

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

  In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be suitably used from the viewpoint of completely removing the binder and / or dye in the light non-irradiated part by development.

  In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.

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

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

  Among these, as colorants, 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.

  As a colorant that can be used in the photopolymerizable composition, a dye or an average particle diameter r (unit: nm) is 20 ≦ r ≦ 300, preferably 125 ≦ r ≦ 250, particularly preferably 30 ≦ r ≦ 200. A pigment that satisfies the above conditions is desirable. By using a pigment having such an average particle diameter r, red and green pixels having a high contrast ratio and a high light transmittance can be obtained. Here, the “average particle size” means the average particle size of secondary particles in which primary particles (single crystallites) of the pigment are aggregated.

  The particle size distribution of the secondary particles of the pigment that can be used in the present invention (hereinafter, simply referred to as “particle size distribution”) is 70% by mass of secondary particles having an average particle size of ± 100 nm. As mentioned above, it is desirable that it is 80 mass% or more.

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

  As content of the coloring agent contained in a photopolymerizable composition, it is preferable that it is 50 to 90 mass% in the total solid of a photopolymerizable composition, and is 55 to 85 mass%. It is preferable that it is 60 mass% or more and 80 mass%.

  If the amount of the colorant is too small, there is a tendency that an appropriate chromaticity cannot be obtained when a color filter is produced from the photopolymerizable composition. On the other hand, if the amount is too large, photocuring does not proceed sufficiently and the strength as a film is reduced, and the development latitude during alkali development tends to be narrow. However, (A) the specific oxime compound in the present invention Since the absorption efficiency is high, even when the colorant is contained in the photopolymerizable composition at a high concentration, the sensitivity improvement effect is remarkably exhibited.

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

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

The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be 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 series), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (azo) "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 dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.

  As content of the dispersing agent in a photopolymerizable composition, it is preferable that they are 1 mass% or more and 80 mass% or less with respect to a pigment, 5 mass% or more and 70 mass% or less are more preferable, and 10 mass% or more and 60 or less. A mass% or less is more preferable.

Specifically, if a polymer dispersant is used, the amount used is preferably in the range of 5% by mass to 100% by mass with respect to the pigment, and in the range of 10% by mass to 80% by mass. Is more preferable.
In the case of using a pigment derivative, the amount used is preferably in the range of 1% by mass to 30% by mass and preferably in the range of 3% by mass to 20% by mass with respect to the pigment. Is more preferable, and is particularly preferably in the range of 5% by mass to 15% by mass.

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

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

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

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

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

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

In General Formula (e-2), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ² —. Here, L ² represents —O— or —S—. Moreover, W is synonymous with what was shown to Formula (e-1).

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

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

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

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

In general formula (IV), R ⁴⁰¹ and R ⁴⁰² each independently represent a monovalent substituent, and R ⁴⁰³ , R ⁴⁰⁴ , R ⁴⁰⁵ and R ⁴⁰⁶ each independently represent a hydrogen atom or a monovalent substituent. To express. n ₄ represents an integer of 0 to 5, n ₄ ′ represents an integer of 0 to 5, and n ₄ and n ₄ ′ cannot both be 0. When n ₄ is 2 or more, a plurality of R ⁴⁰¹ may be the same or different. When n ₄ ′ is 2 or more, a plurality of R ⁴⁰² may be the same or different. In the general formula (IV), the isomer by the double bond is not limited to either one.

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

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

In General Formula (V), A ⁵ represents an aromatic ring or a hetero ring that may have a substituent, X ⁵ represents an oxygen atom, a sulfur atom, or —N (R ⁵⁰³ ) —, and Y ⁵⁰¹ represents An oxygen atom, a sulfur atom, or -N ( ^R503 )-is represented. R ⁵⁰¹ , R ⁵⁰² , and R ⁵⁰³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A ⁵ , R ⁵⁰¹ , R ⁵⁰² , and R ⁵⁰³ are bonded to each other to form an aliphatic group Or aromatic rings may be formed.

In the general formula (V), R ⁵⁰¹ , R ⁵⁰² and R ⁵⁰³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group. When R ⁵⁰¹ , R ⁵⁰² and R ⁵⁰³ represent a monovalent nonmetallic atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group It is preferably a heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.

In the compound represented by the general formula (V), Y ⁵⁰¹ is preferably an oxygen atom or —N (R ⁵⁰³ ) — from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator. R ⁵⁰³ independently represents a hydrogen atom or a monovalent nonmetallic atomic group. Further, Y is most preferably —N (R ⁵⁰³ ) —.

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

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

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

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

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

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

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

In General Formula (VI), X ⁶ represents a sulfur atom, an oxygen atom, or —N (R ⁶⁰³ ) —, and R ⁶⁰³ represents a hydrogen atom having 1 to 5 carbon atoms or an aryl having 6 to 13 carbon atoms. Represents a group. R ⁶⁰¹ and R ⁶⁰² 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 ⁶⁰¹ , R ⁶⁰² and a double bond to which these are bonded May form a benzene ring, and the double bond to which R ⁶⁰¹ and R ⁶⁰² 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 photopolymerizable composition is preferably one represented by the following general formula (V).

In General Formula (VII), R ⁷⁰¹ represents an alkyl group or an aryl group, and A ⁷ represents an atomic group that forms a heterocycle with N═C—N.

In General Formula (VII), R ⁷⁰¹ represents an alkyl group or an aryl group.
^Examples of the alkyl group represented by R ⁷⁰¹ include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear or carbon atom having 1 to 12 carbon atoms. A branched alkyl group having 3 to 12 atoms and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group. , Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group , 2-norbornyl group and the like.

As the aryl group represented by R ⁷⁰¹ , in addition to a monocyclic structure, one to three benzene rings form a condensed ring, or a benzene ring and a five-membered unsaturated ring form a condensed ring Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenabutenyl group, a fluorenyl group, and the like. Among these, a phenyl group and a naphthyl group are exemplified. More preferred.

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

In General Formula (VII), A ⁷ represents an atomic group that forms a heterocycle with N═C—N.
Examples of atoms constituting this atomic group include a carbon atom, a nitrogen atom, a hydrogen atom, a sulfur atom, and a selenium atom.
The heterocyclic ring formed by A ⁷ and N═C—N may further have a substituent, and the substituent that can be introduced is a substituent that can be introduced into the alkyl group or aryl group. The same thing is mentioned.

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

In General Formula (VIII), R ⁸⁰¹ represents an aryl group, and X ⁸ represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an aryl group.

In General Formula (IX), R ⁹⁰¹ represents an alkyl group or an aryl group, and X ⁹ represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an aryl group.

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

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

The alkyl group in general formula (VIII) and (IX) is synonymous with the alkyl group represented by ^R701 in general formula (VII), and its preferable range is also the same.
Further, the aryl group in the general formula ((VIII) and (IX) has the same meaning as the aryl group represented by ^{R 701} in formula (VII), is the same preferred ranges thereof.

Each group in the general formulas (VIII) and (IX) may further have a substituent, and the substituent is introduced into the alkyl group or aryl group represented by ^R701 in the general formula (VII). Similar to those listed as possible substituents.

X ⁸ in general formula (VIII) and X ⁹ in general formula (IX) are more preferably a hydrogen atom from the viewpoint of PGMEA solubility.
In general formula (VIII), R ⁸⁰¹ is most preferably a phenyl group from the viewpoints of sensitivity and PGMEA solubility.
In general formula (IX), R ⁹⁰¹ is more preferably a methyl group, an ethyl group, a phenyl group or a benzyl group from the viewpoint of sensitivity and PGMEA solubility.

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

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

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

-Solubility measurement method-
In this specification, the solubility of the thiol compound is defined as follows: When a specific thiol compound is added to 5 mL of propylene glycol monomethyl ether acetate (PGMEA) solvent and stirred at 25 ° C. for 1 hour, the specific thiol compound does not dissolve. Was the solubility.

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

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

  When the photopolymerizable composition 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 mass of the photopolymerizable composition, The range of 0.5 mass% or more and 30 mass% or less is preferable, the range of 1 mass% or more and 25 mass% or less is more preferable, and the range of 3 mass% or more and 20 mass% or less is still more preferable.

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

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

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

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

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

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

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

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

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

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

<(H) Polymerization inhibitor>
In the photopolymerizable composition, during the production or storage of the photopolymerizable composition, (B) a small amount of thermal polymerization inhibitor is used to prevent unnecessary thermal polymerization of the polymerizable compound such as the specific photopolymerizable compound. It is desirable to add.

  Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

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

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

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

  The addition amount of the adhesion improver is preferably 0.5% by mass or more and 30% by mass or less, and more preferably 0.7% by mass or more and 20% by mass or less in the total solid content of the photopolymerizable composition.

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

<(K) Other additives>
Furthermore, in order to improve the physical properties of the cured film, known additives such as inorganic fillers, plasticizers, and oil sensitizers may be added to the photopolymerizable composition.
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.

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

  Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

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

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

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

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

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

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

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

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

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

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

  In the method for producing a color filter of the present invention, after the colored photopolymerizable composition layer forming step, the exposure step, and the developing step described above are performed, the formed colored pattern is heated and / or if necessary. A curing step of curing by exposure may be included.

  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.

  The photopolymerizable composition for a color filter of the present invention is a composition that cures with high sensitivity even when it contains a colorant at a high concentration and has excellent removability (developability) for an uncured portion. . For this reason, the color filter obtained by using the photopolymerizable composition for a color filter of the present invention has a high-resolution colored pattern having a desired cross-sectional shape, and is developed in a region where the colored pattern is not formed. Residue is effectively suppressed.

  Accordingly, the color filter of the present invention 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.

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

  First, the detail of the specific oxime compound (compounds 1-7) and the compound for a comparison (comparative compounds 1-2) used for the Example and the comparative example is shown below.

  The structures of the compounds used as Comparative Compound 1 and Comparative Compound 2 are as follows.

  A synthesis example of Compound 7 is shown below. Other compounds can be synthesized in the same manner as compound 6.

(Synthesis Example 1: Synthesis of Compound 6)
Ethylcarbazole (100.0 g, 0.512 mol) is dissolved in 260 ml of chlorobenzene, and after cooling to 0 ° C., aluminum chloride (70.3 g, 0.527 mol) is added. Subsequently, o-tolyl chloride (81.5 g, 0.527 mol) is added dropwise over 40 minutes, the temperature is raised to room temperature, and the mixture is stirred for 3 hours. Next, after cooling to 0 ° C., aluminum chloride (75.1 g, 0.563 mol) is added. 4-Chlorobutyryl chloride (79.4 g, 0.563 mol) is added dropwise over 40 minutes, and the mixture is warmed to room temperature and stirred for 3 hours. A mixed solution of 156 ml of 35 wt% hydrochloric acid aqueous solution and 392 ml of distilled water is cooled to 0 ° C., and the reaction solution is added dropwise. The precipitated solid was filtered with suction, washed with distilled water and methanol, and recrystallized with acetonitrile to obtain Compound A (yield 164.4 g, yield 77%) having the following structure.

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

  Compound B (18.0 g, 32.4 mmol) was dissolved in 90 ml N-methylpyrrolidone and triethylamine (3.94 g, 38.9 mmol) was added. Next, after cooling to 0 ° C., acetyl chloride (3.05 g, 38.9 mmol) is added dropwise over 20 minutes, and then the temperature is raised to room temperature and stirred for 2 hours. The reaction solution was added dropwise to 150 ml of distilled water cooled to 0 ° C., and the precipitated solid was subjected to suction filtration, washed with 200 ml of isopropyl alcohol cooled to 0 ° C., dried, and then compound 6 (yield 19.5 g, yield 99%). )

Moreover, the structure of the obtained compound 6 was identified by NMR.
( ¹ H-NMR 400 MHz CDCl 3): 8.86 (s, 1H), 8.60 (s, 1H), 8.31 (d, 1H, J = 8.0 Hz), 8.81 (d, 1H, J = 8.0 Hz), 7.51-7.24 (m.10H), 7.36 (q, 2H, 7.4 Hz), 3.24-3.13 (m, 4H), 2.36 ( s, 3H), 2.21 (s, 3H), 1.50 (t, 3H, 7.4 Hz).

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

1-1. Preparation of pigment dispersion (P1) C.I. I. Pigment Green 36 and C.I. I. 40 parts by mass of a 30/70 (mass ratio) mixture with CI Pigment Yellow 219, and 10 parts by mass (solid content conversion: about 4.4 by dispersbyk: manufactured by BYK Corporation, 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 a colored photopolymerizable composition A-1.

<Composition A-1>
-Pigment dispersion (P1) 700 parts by mass-Alkali-soluble resin 100 parts by mass (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10, Mw: 10,000)
Polyfunctional monomer (Exemplary compound (A-2), specific photopolymerizable compound) 60 parts by mass Compound 1 (specific oxime compound) 60 parts by mass Solvent: 1000 parts by mass of propylene glycol monomethyl ether acetate Agent (trade name: Tetranic 150R1, BASF) 1 part by mass / γ-methacryloxypropyltriethoxysilane 5 parts by mass

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

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

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

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

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

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

3-2. Exposure Sensitivity of 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, cross-sectional shape of pattern, coloring evaluation over time with forced heating Confirm substrate surface and cross-sectional shape after post-baking in “2-3. Heat treatment” by optical microscope and SEM photograph observation by a normal method. Thus, developability and pattern cross-sectional shape were evaluated. Details of the evaluation method are as follows.

<Developability (confirmation of development residue)>
In the exposure step, the developability was evaluated by observing the presence or absence of development residues in a region not irradiated with light (unexposed portion). The results are shown in Table 1 below.
-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

<Pattern cross-sectional shape>
The cross-sectional shape of the formed pattern was observed and evaluated. The cross-sectional shape of the pattern is most preferably a forward taper, and a rectangular shape is next preferred. Reverse taper is not preferred. The results are shown in Table 1 below.

[Examples 1-2 to 1-25, Comparative Examples 1-1 to 1-11]
In composition A-1 used for preparation of colored photopolymerizable composition A-1 in Example 1-1, 60 parts by mass of compound 1 (specific oxime compound) and a polyfunctional monomer (specific photopolymerizable compound) 60 mass parts of a certain exemplary compound (A-2) is replaced with each compound and amount shown in the following Tables 1 to 3, and Examples 18 to 28 are further sensitizers and / or co-sensitizers. The photopolymerizable compositions A-2 to A-25 and A'-1 to A 'were used in the same manner as in Example 1-1 except that were added in the types and amounts shown in Tables 1 to 3 below. '-11 was prepared. Furthermore, a color filter was produced using these colored photopolymerizable compositions.
The same evaluation as Example 1 was performed about the obtained colored photopolymerizable composition and color filter. The results are shown in Tables 1 to 3.

  Sensitizers A1 to A3 and cosensitizers F1 to F3 shown in Table 2 are the compounds shown below.

  From the results of Tables 1 to 3, the photopolymerizable compositions of the Examples containing the specific oxime compounds (Compounds 1 to 7) have high exposure sensitivity, and development when using a color filter color pattern for formation. It can be seen that it is excellent both in the property (suppression of occurrence of development residue), the evaluation of coloring of the obtained colored pattern with forced heating, and the cross-sectional shape of the pattern. Moreover, it turns out that the photopolymerizable composition of each Example is excellent in storage stability (aging stability).

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

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

[3. Preparation of colored photopolymerizable composition B-1]
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 / polyfunctional monomer (Exemplary Compound (A-2), specific photopolymerizable compound) 7.0 parts by mass / Compound 1 (specific oxime compound) 2.5 parts by mass / glycerol Propoxylate (number average molecular weight Mn: 1500) 0.5 parts by mass

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

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

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

<Exposure sensitivity>
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 polymerizability and the better the sensitivity.
The results are shown in 4 below.

<Pattern cross-sectional shape>
The pattern cross-sectional shape was evaluated based on the evaluation method and evaluation criteria performed on Example 1-1. The results of measurement evaluation are shown in Table 5 below.

-Confirmation of development residue-
Using a length measurement SEM (Hitachi S-9260S), observe the pattern peripheral part of a 1.5 μm square pixel pattern at an exposure amount of 7000 J / m ² , and between patterns (colored pattern non-formation region). The occurrence of the kimono and undissolved residue, that is, the development residue was observed.
The observed results were evaluated by classifying them into three stages of Type-A, Type-B, and Type-C in order from the most appropriate level (that is, in order from the order in which the generation of the residue is suppressed). Details of the classification method are shown in Table 4 below. Moreover, the generation | occurrence | production state of the development residue in Type-A, Type-B, and Type-C is shown in FIG.

[Examples 2-2 to 2-25, comparative examples 2-1 to 2-7]
In Example 2-1, 2.5 parts by mass of compound 1 (specific oxime compound) in composition B-1 used for the preparation of colored photopolymerizable composition B-1 and a polyfunctional monomer (specific photopolymerization) Example compound (A-2)) 7.0 parts by mass is replaced with the respective compounds and amounts shown in Tables 5 to 7 below, and Examples 2-17 to 2-25 are also shown in the following table. 5 to 7 except that sensitizers and / or co-sensitizers shown in Table 7 were added in the types and amounts shown in Tables 5 to 7 below. Sex compositions B-2 to B-25 and B′-1 to B′-7 were prepared. Furthermore, a color filter was produced using these colored photopolymerizable compositions.
The same evaluation as Example 2-1 was performed about the obtained colored photopolymerizable composition and color filter. The results are shown in Tables 5-7.

  Sensitizers A1 to A3 and cosensitizers F1 to F3 shown in Table 6 are the compounds described above.

  From the results of Tables 5 to 7, the colored photopolymerizable compositions of the Examples containing the specific oxime compounds (Compounds 1 to 7) have high exposure sensitivity, and are developed when the color filter color pattern is used for the formation. Generation | occurrence | production of a residue is also suppressed and it turns out that the pattern cross-sectional shape of the obtained coloring pattern is also excellent. Moreover, it turns out that these colored photopolymerizable compositions are excellent in storage stability (time stability).

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

<Composition C-1>
-Ethyl 3-ethoxypropionate [solvent] 17.9 parts by mass-Colorant C.I. I. Pigment Red 254 pigment dispersion (solid content: 15%, pigment content in solid content: 60%) 26.7 parts by mass Colorant C.I. I. Pigment Yellow 139 pigment dispersion (solid content: 15%, pigment content in solid content: 60%) 17.8 parts by mass / polyfunctional monomer (exemplary compound (A-2), specific photopolymerizable compound) 3.5 parts by mass [3: 7 mixture of pentaerythritol triacrylate and dipentaerythritol hexaacrylate]
Compound 1 (specific oxime compound) 0.5 parts by mass Benzyl methacrylate / methacrylic acid copolymer 2.0 parts by mass (molar ratio = 70/30)

<Evaluation of storage stability of colored photopolymerizable composition C-1 (coating liquid)>
Storage stability of the colored photopolymerizable composition C-1 (coating solution) in the same manner as in Example 2-1, except that the colored photopolymerizable composition B-1 was replaced with the colored photosensitive composition C-1. Sex was evaluated. The results are shown in Table 8.

<Production and Evaluation of Color Filter Using Colored Photopolymerizable Composition C-1>
A color filter of Example 4-1 was produced in the same manner as in Example 2-1, except that the colored photopolymerizable composition B-1 was replaced with the colored photopolymerizable composition C-1, and Example 2- Evaluation similar to 1 was performed. The results are shown in Table 8 below.

[Examples 3-2 to 3-25, Comparative examples 3-1 to 3-7]
In Example 3-1, 0.5 part by mass of compound 1 (specific oxime compound) in composition C-1 used for the preparation of colored photopolymerizable composition C-1 and a polyfunctional monomer (specific photopolymerization) Example compound (A-2)) 3.5 parts by mass, which is an ionic compound, is replaced with the respective compounds and amounts shown in the following Tables 8 to 10, and further about Examples 3-17 to 3-25, Except that the sensitizers and / or co-sensitizers shown in Tables 8 to 10 were added in the types and amounts shown in the following Tables 8 to 10, all were the same as in Example 3-1, and light was used. Polymerizable compositions C-2 to C-25 and C′-1 to C′-7 were prepared. Furthermore, a color filter was produced using the obtained colored photopolymerizable composition.
The same evaluation as Example 3-1 was performed about the obtained colored photopolymerizable composition and color filter. The results are shown in Tables 8-10.

  Sensitizers A1 to A3 and cosensitizers F1 to F3 shown in Table 9 are the compounds described above.

  From the results of Tables 8 to 10, the colored photopolymerizable compositions of the Examples containing the specific oxime compounds (Compounds 1 to 7) have high exposure sensitivity, and the development residue when the colored pattern of the color filter is used for formation. It can be seen that the occurrence of this is also suppressed, and the pattern cross-sectional shape of the resulting colored pattern is excellent. Moreover, it turns out that these colored photopolymerizable compositions are excellent in storage stability (time stability).

[Example 4-1]
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> (High pigment concentration)
-Ethyl 3-ethoxypropionate [solvent] 17.9 parts by mass-Colorant C.I. I. Pigment Red 254 pigment dispersion (solid content: 15%, pigment content in solid content: 60%) 33.34 parts by mass Colorant C.I. I. Pigment Yellow 139 pigment dispersion (solid content: 15%, pigment content in solid content: 60%) 22.23 parts by mass / polyfunctional monomer (exemplary compound (A-2), specific photopolymerizable compound ) 2.5 parts by mass · Compound 1 (specific oxime compound) 0.5 parts by mass · 2.0 parts by mass of benzyl methacrylate / methacrylic acid copolymer (molar ratio = 70/30)

<Evaluation of storage stability of colored photopolymerizable composition D-1 (coating liquid)>
Storage stability of the colored photopolymerizable composition D-1 (coating liquid) in the same manner as in Example 2-1, except that the colored photopolymerizable composition B-1 was replaced with the colored photosensitive composition D-1. Sex was evaluated. The results are shown in Table 11.

<Production and Evaluation of Color Filter Using Colored Photopolymerizable Composition D-1>
A color filter of Example 4-1 was produced in the same manner as in Example 2-1, except that the colored photopolymerizable composition B-1 was replaced with the colored photopolymerizable composition D-1, and Example 2- Evaluation similar to 1 was performed. The results are shown in Table 8 below.

[Examples 4-2 to 4-18, Comparative examples 4-1 to 4-7]
In Example 4-1, 2.5 parts by mass of compound 1 (specific oxime compound) in composition D-1 used for the preparation of colored photopolymerizable composition D-1 and a polyfunctional monomer (specific photopolymerization) Example compound (A-2)) 2.5 parts by mass, which is an ionic compound, is replaced with the respective compounds and amounts shown in Tables 11 to 13 below, and for Examples 4-10 to 4-18, Except that the sensitizers and / or co-sensitizers shown in the following Tables 11 to 13 were added in the types and amounts shown in the following Tables 11 to 13, the same procedure as in Example 4-1 was conducted. Polymerizable compositions D-2 to D-18 and D′-1 to D′-7 were prepared. Furthermore, a color filter was produced using the obtained colored photopolymerizable composition. Furthermore, evaluation similar to Example 2-1 was performed about the obtained colored photopolymerizable composition and color filter.

  Sensitizers A1 to A3 and cosensitizers F1 to F3 shown in Table 12 are the compounds described above.

  From the results of Tables 11 to 13, the colored photopolymerizable compositions of the Examples containing the specific oxime compounds (Compounds 1 to 7) have high exposure sensitivity, and when the colored pattern of the color filter was used for the formation. Generation | occurrence | production of the image development residue is also suppressed and it turns out that the pattern cross-sectional shape of the obtained coloring pattern is also excellent. Moreover, it turns out that these colored photopolymerizable compositions are excellent in storage stability (time stability).

In an Example, it is a figure which shows the classification | category method of the generation | occurrence | production state of the development residue.

Claims (7)

(A) a compound represented by the following general formula (I), (B) a polyfunctional photopolymerizable compound having one or more acidic functional groups and / or one or more alkyleneoxy chains, and (C) a colorant A photopolymerizable composition for a color filter, comprising:

[In General Formula (I), R and B each independently represent a monovalent organic group, X represents a monovalent substituent, Y ¹ and Y ² each independently represent a monovalent substituent, n ₁ represents an integer of 0-4. ] 2. The photopolymerizable composition for a color filter according to claim 1, wherein the compound represented by (A) the general formula (I) is a compound represented by the following general formula (II).

[In General Formula (II), R and B each independently represent a monovalent organic group, Z represents a monovalent substituent, and n ₂ represents an integer of 0 to 5. ] The polyfunctional photopolymerizable compound (B) having one or more acidic functional groups and / or one or more alkyleneoxy chains is represented by the following general formula (1), general formula (2), or general formula (3). The photopolymerizable composition for a color filter according to claim 1, wherein the photopolymerizable composition is a compound represented by the formula:

[In General Formula (1), R ¹ , T ¹ , and X ¹ each independently represent any of the groups shown below as R ¹ , T ¹ , or X ¹ . n represents an integer of 0 to 14. ]

[In General Formula (2), Z ¹ and G ¹ each independently represent any of the groups shown below as Z ¹ or G ¹ . W ¹ is synonymous with the group represented by R ¹ or X ¹ in the general formula (1), and 3 or more of 6 W ¹ represent R ¹ . p represents an integer of 0 to 14. ]

[In General Formula (3), each R ² independently represents a substituent containing an ethylenic double bond or a substituent containing a hydroxy group, and at least one of a plurality of R ² is present in the structure. Has an alkylene oxide chain. ]   The content of the (C) colorant is 50% by mass or more and 90% by mass or less with respect to the total solid content of the photopolymerizable composition. Item 4. A photopolymerizable composition for a color filter according to item.   It has a coloring pattern which uses the photopolymerizable composition for color filters of any one of Claims 1-4, The color filter characterized by the above-mentioned. Applying the photopolymerizable composition for a color filter according to any one of claims 1 to 4 on a support to form a photopolymerizable composition layer;
Exposing the photopolymerizable composition layer through a mask;
Developing the photopolymerizable composition layer after exposure to form a colored pattern; and
A method for producing a color filter, comprising:   A solid-state imaging device comprising the color filter according to claim 5.

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