JP2010204213A - Photopolymerizable composition, photopolymerizable composition for color filter, color filter and production method thereof, solid-state image pickup device, and lithographic printing plate precursor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photopolymerizable composition having high sensitivity to light at a wavelength of 365 nm or 405 nm and excellent properties of a coating surface and capable of giving a cured film having a smooth surface, and to provide a color filter and a lithographic printing plate precursor using the composition. <P>SOLUTION: The photopolymerizable composition contains photopolymerizable initiators expressed by general formula (1) and general formula (2). In the general formulae (1) and (2), B<SP>1</SP>, B<SP>2</SP>, R<SP>1</SP>, X<SP>1</SP>and X<SP>2</SP>each represents a monovalent substituent; A represents a divalent organic group; Ar<SP>1</SP>represents an aryl group; Y represents a monovalent substituent including a partial structure having a polymerization initiating ability; and m and n each represents an integer of 0 to 5. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

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

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

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

On the other hand, a color filter for an image sensor has a strong demand for a high color density and a thin film of the color filter in order to improve image quality due to high light condensing property and high color separation of a solid-state imaging device such as a CCD. When a large amount of coloring material is added to obtain a high coloring density, the sensitivity is insufficient to faithfully reproduce the shape of a fine pixel pattern of 2.5 μm or less, and overall pattern loss tends to occur frequently. There is. In order to eliminate this loss, it is necessary to irradiate light with higher energy, so that the exposure time becomes longer and the manufacturing yield is significantly reduced. From the above, the colored radiation-sensitive composition for color filters has high sensitivity because it is necessary to obtain good pattern formability while containing a colorant (colorant) at a high concentration. It is the present situation that this is desired. However, when the content of the oxime ester compound is increased in order to improve sensitivity, there arises a problem that the coated surface property of the photopolymerizable composition is lowered due to the solubility of the oxime ester compound.
Thus, an oxime ester compound having excellent reactivity has been proposed, and a plurality of initiators having different structures are used in combination (see Patent Document 6). However, the sensitivity is still not sufficient, and there is a point to be improved in the coated surface property.

US Pat. No. 4,255,513 US Pat. No. 4,590,145 JP 2000-80068 A JP 2001-233842 A JP 2006-195425 A JP 2006-36750 A

The first object of the present invention is to provide a photopolymerizable composition that can be cured with high sensitivity to light having a wavelength of 365 nm or 405 nm, and can form a cured film having excellent coated surface properties and a smooth surface. There is.
A second object of the present invention is to provide a photopolymerizable composition for a color filter that can be cured with high sensitivity, has good pattern forming properties, and can form a colored pattern with a uniform film thickness.
Furthermore, a third object of the present invention is to provide a color filter comprising a colored pattern having a good pattern shape and excellent film thickness uniformity, using the photopolymerizable composition for a color filter, and Another object of the present invention is to provide a manufacturing method capable of manufacturing a color filter with high productivity, and further to provide a solid-state imaging device including the color filter.
In addition, a fourth object of the present invention is to provide a lithographic printing plate that uses the above-mentioned photopolymerizable composition for a photosensitive layer and can obtain a lithographic printing plate having high sensitivity and excellent film thickness uniformity and printing durability. The purpose is to provide a printing plate precursor.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using two kinds of oxime compounds having a specific partial structure and different structures, and the present invention has been completed. did. That is, the configuration of the present invention is as follows.
<1> A photopolymerizable composition containing a photopolymerization initiator represented by the following general formula (1) and a photopolymerization initiator represented by the following general formula (2).

[In formula ^{(1), B 1, R} 1 and ^{X 1} each independently represent a monovalent substituent, A represents a divalent organic group, Ar ¹ represents an aryl group. n is an integer of 0-5.
In the general formula (2), B ² and X ² each independently represent a monovalent substituent. Y represents a monovalent substituent including a partial structure having a polymerization initiating ability. m is an integer of 0-5. ]
<2> The photopolymerizable composition according to <1>, wherein the photopolymerization start represented by the general formula (2) is a compound represented by the following general formula (3).

[In the above general formula (3), B ² , R ^2, X ² and Z each independently represent a monovalent substituent. m is an integer of 0-5. ]
<3> The photopolymerizable composition according to <2>, wherein the photopolymerization start represented by the general formula (3) is a compound represented by the following general formula (4).

[In the general formula (4), B ² , R ² and X ² each independently represent a monovalent substituent, E represents a divalent organic group, and Ar ² represents an aryl group. m is an integer of 0-5. ]
<4> The photoheavy composition according to any one of <1> to <3>, further comprising (B) a polymerizable compound.
<5> The photopolymerizable composition according to <4>, further comprising (C) a colorant.
<6> The photopolymerizable composition according to <5>, wherein the (C) colorant is a pigment, and (D) further contains a pigment dispersant.
<7> A photopolymerizable composition for a color filter containing the photopolymerizable composition according to any one of <5> or <6>.

<8> A color filter having a colored pattern formed using the photopolymerizable composition for a color filter according to <7> on a support.
<9> A step of applying a photopolymerizable composition for a color filter according to <7> on a support to form a photopolymerizable composition layer, and a step of pattern exposing the photopolymerizable composition layer And a step of developing the photopolymerizable composition layer after exposure to form a colored pattern, and a method for producing a color filter.
<10> A solid-state imaging device including the color filter according to <8>.
<11> A lithographic printing plate precursor comprising a photosensitive layer containing the photopolymerizable composition according to <4> on a support.

ADVANTAGE OF THE INVENTION According to this invention, the sensitivity with respect to the light of wavelength 365nm or 405nm is high, and the photopolymerizable composition which can form the cured film excellent in the coated surface property can be provided.
Further, according to the present invention, it is possible to provide a photopolymerizable composition for a color filter that can be cured with high sensitivity, has a good pattern forming property, and can form a colored pattern with excellent film thickness uniformity. .
Furthermore, according to the present invention, a color filter comprising the above-mentioned photopolymerizable composition for a color filter, having a good pattern shape and a colored pattern having no variation in film thickness, and a high color filter. A manufacturing method that can be manufactured with productivity, and a solid-state imaging device including the color filter can be provided.
In addition, according to the present invention, a lithographic printing plate precursor capable of obtaining a lithographic printing plate having high sensitivity, excellent film thickness uniformity and printing durability, using the photopolymerizable composition as a photosensitive layer. Can be provided.

<Photopolymerizable composition>
The photopolymerizable composition of the present invention is represented by a photopolymerization initiator represented by the following general formula (1) (hereinafter referred to as “initiator (1)” as appropriate) and a general formula (2). A polymerization initiator (hereinafter appropriately referred to as “initiator (2)”).
First, the photopolymerization initiator [initiator (1)] represented by the general formula (1) will be described.

In the general formula (1), B ¹ , R ¹ and X ¹ each independently represent a monovalent substituent, A represents a divalent organic group, and Ar ¹ represents an aryl group. n is an integer of 0-5.

The monovalent substituent represented by R ¹ is preferably a monovalent nonmetallic atomic group shown below.
Examples of the monovalent nonmetallic atomic group represented by R ¹ 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 group, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent. An arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, and a substituent May have a 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, or a substituent. Dialkylaminoca Examples thereof include a sulfonyl group and a dialkylaminothiocarbonyl group which may have a substituent, and an acyl group, an alkoxycarbonyl group and the like are preferable.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms. For example, an acetyl group, a propanoyl group, a butanoyl group, a trifluoromethylcarbonyl group, a pentanoyl group, a 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-methoxy Benzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxy A benzoyl group etc. are mentioned.

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

Among these, from the viewpoint of increasing sensitivity, R ¹ is more preferably an acyl group, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable.

Examples of the divalent organic group represented by A include alkylene having 1 to 12 carbon atoms which may have a substituent, cyclohexylene which may have a substituent, and alkynylene which may have a substituent. Is mentioned.
Among them, A is substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloring due to heating. Alkylene group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl) An alkylene group substituted with a group) is preferred.

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

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

The monovalent substituent represented by X ¹ in the general formula (1) may have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. A good alkenyl group, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, Arylthiooxy group which may have a substituent, acyloxy group which may have a substituent, alkylsulfanyl group which may have a substituent, arylsulfanyl group which may have a substituent, substituent An alkylsulfinyl group that may have a substituent, an arylsulfinyl group that may have a substituent, an alkylsulfonyl group that may have a substituent, an arylsulfonyl group that may have a substituent, and a substituent. Acyl A group, an alkoxycarbonyl group which may have a substituent, a carbamoyl group which may have a substituent, a sulfamoyl group which may have a substituent, an amino group which may have a substituent, a substituent The phosphinoyl group which may have, the heterocyclic group which may have a substituent, a halogen group etc. are mentioned, An alkyl group and an acyl group. An amino group and the like are preferable.

  The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group. , Octadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl Group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group , 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3 Nitorofenashiru 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, an acetyl group, a propanoyl group, a butanoyl group, a trifluoromethylcarbonyl group, a pentanoyl group, a 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-methoxy Benzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxy A benzoyl group etc. are mentioned.

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

Among these, X ¹ has an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent from the viewpoint of solvent solubility and improvement of absorption efficiency in the long wavelength region. An alkenyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio which may have a substituent A xyl group, an arylthioxy group which may have a substituent, and an amino group which may have a substituent are preferable.

The monovalent substituent represented by B ¹ in the general formula (1) is preferably a monovalent nonmetallic atomic group shown below.
Examples of the monovalent nonmetallic atomic group represented by B ¹ 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 group, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent. An arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, and a substituent May have a 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, or a substituent. Dialkylaminoca Examples thereof include a sulfonyl group and a dialkylaminothiocarbonyl group which may have a substituent.
Among these, an unsubstituted alkyl group having 1 to 4 carbon atoms is preferable.
Moreover, although n in General formula (1) represents the integer of 0-5, the integer of 0-2 is preferable.

  Hereinafter, although the specific example of the oxime compound included by the initiator (1) which can be used for this invention is shown below, this invention is not limited to these.

The oxime compound included in the initiator (1) that can be used in the present invention has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm. More preferably, a material having an absorption wavelength in a wavelength region of 360 nm to 480 nm can be exemplified. In particular, those having high absorbance at 365 nm and 455 nm are preferable.
Thus, the oxime compound has an absorption in a long wavelength region as compared with a conventional oxime compound. Therefore, when exposed with a light source of 365 nm or 405 nm, excellent sensitivity is exhibited.

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound included in the initiator (1) according to the present invention is preferably 10,000 to 300,000, more preferably 15,000 to 300,000 from the viewpoint of sensitivity. It is especially preferable that it is 20000-200000.
Here, the molar extinction coefficient of the oxime compound was measured with an ultraviolet-visible spectrophotometer (Carry-5 spectrophotometer manufactured by Varian) at a concentration of 0.01 g / L using an ethyl acetate solvent.

  The content of the initiator (1) in the photopolymerizable composition of the present invention is 0.1 to 50% by mass, more preferably 1 to 40% by mass, based on the total solid content of the photopolymerizable composition. 5 to 30% by mass is particularly preferable.

  The oxime compound which is the initiator (1) according to the present invention is decomposed by light and initiates and accelerates polymerization of the polymerizable compound, but has excellent sensitivity to a light source of 365 nm or 405 nm.

Next, the photopolymerization initiator [initiator (2)] represented by the general formula (2) will be described.
The initiator (2) is a compound represented by the following general formula (2).

In the general formula (2), B ² and X ² each independently represent a monovalent substituent. Y represents a monovalent substituent including a partial structure having a polymerization initiating ability.
Here, B ² and X ² are respectively synonymous with B ¹ and X ¹ in the general formula (1), and preferred examples are also the same.
m is an integer of 0 to 5, preferably an integer of 0 to 2.

  In addition, the monovalent substituent represented by Y is not particularly limited as long as it includes a partial structure having a polymerization initiating ability, and the partial structure having a polymerization initiating ability is a structure having a known initiating ability. Any of them can be used, but from the viewpoint of compatibility and sensitivity, it is preferable that the oxime structure is preferably used as a partial structure having a polymerization initiating ability. From such a viewpoint, the photopolymerization initiator represented by the general formula (2) is preferably a compound represented by the following general formula (3), and a compound represented by the following general formula (4) It is more preferable that

上記一般式（３）中、Ｂ^２、Ｘ^２及びｍは、前記一般式（２）におけるのと同義である。
Ｚは、一価の置換基を表し、具体的には、置換基を有していてもよいアルキル基、アリール基、ヘテロアルキル基、ヘテロアリール基などが挙げられ、好ましくは、アルキレン基、アリーレン基、及びヘテロ原子を含むアルキレン基などの２価の基を介して、アリール基やヘテロアリール基が結合している置換基を表す。
ｍは０〜５の整数であり、好ましくは０〜２の整数である。
Ｒ^２は、一般式（１）におけるＲ^１と同義であり、好ましい例も同様である。

In the general formula (3), B ² , X ² and m have the same meaning as in the general formula (2).
Z represents a monovalent substituent, and specific examples include an alkyl group, aryl group, heteroalkyl group, heteroaryl group and the like, which may have a substituent, preferably an alkylene group, arylene And a substituent to which an aryl group or heteroaryl group is bonded via a group and a divalent group such as an alkylene group containing a hetero atom.
m is an integer of 0 to 5, preferably an integer of 0 to 2.
R ² has the same meaning as ^{R 1} in the general formula (1), and preferred examples are also the same.

上記一般式（４）中、Ｂ^２、Ｒ^２、Ｘ^２、及びｍは、それぞれ、一般式（１）におけるＢ^１、Ｒ^１、Ｘ^１及びｎと同義である。Ｅは二価の有機基を表し、一般式（１）におけるＡと同義であり、好ましい例も同様である。Ａｒ^２はアリール基を表し、一般式（１）におけるＡｒ^１と同様であり、好ましい例も同様である。
この一般式（４）で示される化合物は、前記一般式（１）で示されるのと同様の構造を有する開始剤であり、このように、本発明においては、同様のケトオキシム構造と部分骨格を有し、且つ、ここで示される−（Ｘ^２）ｍ、−Ｂ^２、−ＯＲ^２及びＥの少なくとも１つが異なる化合物を組み合わせて用いることが好ましい。
より具体的には、一般式（１）で示される具体的に使用される化合物と、該一般式（１）で示される化合物における−（Ｘ^１）ｍ、−Ｂ^１、−ＯＲ^１及びＡの少なくとも１つが異なる−（Ｘ^２）ｍ、−Ｂ^２、−ＯＲ^２及びＥを備える一般式（４）で示される化合物と、を２種組み合わせる態様がもっとも好ましい。
従って、開始剤（２）に包含される例示化合物としては、前記開始剤（１）で挙げた化合物も同様に挙げられる。
以下、開始剤（２）の例示化合物を挙げるが、本発明はこれらに限定されない。

In the general formula ^{(4), B 2, R} 2, X 2, and m, respectively, ^{B 1,} the same meanings as R 1, ^{X 1} and n in the general formula (1). E represents a divalent organic group and has the same meaning as A in formula (1), and preferred examples are also the same. Ar ² represents an aryl group and is the same as Ar ¹ in the general formula (1), and preferred examples are also the same.
The compound represented by the general formula (4) is an initiator having a structure similar to that represented by the general formula (1). Thus, in the present invention, a similar ketoxime structure and partial skeleton are formed. It is preferable to use a combination of compounds having at least one of — (X ² ) m, —B ² , —OR ^2, and E, which are different from each other.
More specifically, the specifically used compound represented by the general formula (1) and-(X ¹ ) m, -B ¹ , -OR ¹ and A in the compound represented by the general formula (1) An embodiment in which two kinds of compounds represented by the general formula (4) having at least one of-(X ² ) m, -B ² , -OR ² and E are combined is most preferable.
Therefore, examples of the compound included in the initiator (2) include the same compounds as those exemplified in the initiator (1).
Hereinafter, although the exemplary compound of an initiator (2) is given, this invention is not limited to these.

In the initiator (2) according to the present invention, the molar extinction coefficient at 365 nm or 405 nm is preferably 10,000 to 300,000, more preferably 15,000 to 300,000, from 20000 to 200,000, from the viewpoint of sensitivity. It is particularly preferred.
Here, the molar extinction coefficient of the oxime compound was measured with an ultraviolet-visible spectrophotometer (Carry-5 spectrophotometer manufactured by Varian) at a concentration of 0.01 g / L using an ethyl acetate solvent.

  The content of the initiator (2) in the photopolymerizable composition of the present invention is 0.1 to 50% by mass, more preferably 1 to 40% by mass, based on the total solid content of the photopolymerizable composition. -30 mass% is particularly preferred.

  The initiator (2) according to the present invention is decomposed by light and initiates and accelerates polymerization of the polymerizable compound, but has excellent sensitivity to a light source of 365 nm or 405 nm.

  In the present invention, as described above, it is important to use two kinds of polymerization initiators having the same or very similar partial structure and different structures from each other. That is, by having a similar skeleton, the photopolymerizable composition contains two kinds of initiators, but the composition becomes uniform and compatibility with other components of the polymerizable composition is improved. The improvement in sensitivity is achieved while suppressing a decrease in the coating surface property often caused by increasing the content of the initiator.

The content ratio of the initiator (1) to the initiator (2) is not particularly limited, but is preferably in the range of 90:10 to 10:90, and in the range of 80:20 to 20:80. More preferably.
Moreover, although the preferable addition amount of initiator (1) and initiator (2) is as above-mentioned, as total amount of both, it is 0.2-50 mass% in the total solid of a photopolymerizable composition. 1 to 40% by mass is more preferable, and 2 to 30% by mass is particularly preferable.

  The photopolymerizable composition of the present invention has a high sensitivity to light having a wavelength of 365 nm or 405 nm, and can form a cured film having excellent coated surface properties. Although the detailed mechanism is unknown, the oxime compound having a specific structure as the initiator (1) has a structure that absorbs light and suppresses radical recombination when cleaved, so that the amount of generated radicals is large. High sensitivity can be achieved. By using this in combination with a second initiator having a similar skeleton [initiator (2)], the compatibility between the initiator and the other components contained in the polymerizable composition and the initiator is improved. This improves the uniformity of the composition, and the initiator is uniformly present in the composition. Therefore, it is considered that higher sensitivity has been achieved.

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

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

-Photopolymerizable composition (1)-
[(1)-(A) Photopolymerization initiator]
The photopolymerization initiator (A) contained in the photopolymerizable composition (1) is an oxime compound that is the initiator (1), a compound having a similar skeleton to the initiator (1), and a different compound. And initiator (2). As described above, the content ratio of both is preferably 90:10 to 10:90.
The total content of the initiator (1) and the initiator (2) in the photopolymerizable composition (1) is preferably 0.5 to 50% by mass, and 1 to 40% by mass with respect to the total solid content of the composition. % Is more preferable, and 1.5 to 30% by mass is still more preferable.

The photopolymerizable composition (1) may be used in combination with a known photopolymerization initiator other than the initiator (1) and the initiator (2) as long as the effects of the present invention are not impaired.
The photopolymerization initiator that can be used in combination is a compound that is decomposed by light and starts and accelerates polymerization of a polymerizable compound described later, and preferably has absorption in a wavelength region of 300 to 500 nm. Specifically, for example, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, biimidazole compounds Organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

[(1)-(B) polymerizable compound]
The photopolymerizable composition (1) preferably contains (B) a polymerizable compound. The polymerizable compound (B) that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. Chosen from. 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.

  Examples of the other esters include, for example, 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- Those having an aromatic skeleton described in 226149, those containing an amino group described in JP-A-1-165613, and the like are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

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

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

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

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

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

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

[(1)-(C) Colorant]
The photopolymerizable composition (1) can contain a colorant (C). By containing a colorant, a colored photopolymerizable composition having a desired color can be obtained.
The photopolymerizable composition (1) contains an oxime compound having excellent sensitivity to a 365 nm or 406 nm light source, which is a short wavelength light source, as the initiator (1), and therefore contains a colorant in a high concentration. In some cases, it can be cured with high sensitivity.

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

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

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

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

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

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

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Black 1
Alternatively, titanium black [13M-C, 13R-N, Ako Kasei Co., Ltd. Tilack D manufactured by Mitsubishi Chemical Corporation] and the like can be mentioned.

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

  In the photopolymerizable composition (1), when the colorant is a dye, a colored composition in a state of being uniformly dissolved in the composition can be obtained.

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

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

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

The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be 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 (1), it is preferable that it is 1-80 mass% with respect to a pigment, 5-70 mass% is more preferable, 10-60 mass% is still more preferable. .
Specifically, if a polymer dispersant is used, the amount of use thereof is preferably in the range of 5 to 100% by mass, more preferably in the range of 10 to 80% by mass with respect to the pigment.
In the case of using a pigment derivative, the amount used is preferably in the range of 1 to 30% by mass, more preferably in the range of 3 to 20% by mass, based on the pigment, A range of 15% by mass is particularly preferable.

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

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

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

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

  More preferable examples of the sensitizer in the photopolymerizable composition (1) include compounds described in paragraph numbers [0085] to [0098] of JP-A-2008-214395.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The binder polymer that can be used in the present invention can be synthesized by a conventionally known method. 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 (1) include known compounds such as an azo initiator and a peroxide initiator.

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

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

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

  Silane coupling agents include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, and γ-mercaptopropyltrimethoxy. Silane, γ-aminopropyltriethoxysilane, and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane is preferable.

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

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

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

As mentioned above, since the photopolymerizable composition (1) of the present invention contains (A) two specific photopolymerization initiators, it is cured with high sensitivity, and the coated surface property is also good and cured. Excellent film thickness uniformity. In addition, when the photopolymerizable composition (1) is applied to the surface of the hard material and cured, it exhibits high adhesion to the surface due to the characteristics of the initiator (1).
Such a photopolymerizable composition (1) comprises (A) two specific photopolymerization initiators, (B) a polymerizable compound, and (C) a colorant, and a photopolymerizable composition for a color filter. It is preferably used as a product (photopolymerizable composition for a color filter of the present invention).

-Photopolymerizable composition (2)-
[(2)-(A) Photopolymerization initiator]
The photopolymerization initiator contained in the photopolymerizable composition (2) is a combination of (A) two specific photopolymerization initiators as described above.
As described above, the preferable content ratio of the initiator (1) and the initiator (2) in the photopolymerizable composition (2) is in the range of 90:10 to 10:90, and the two kinds of light 0.5-50 mass% is preferable with respect to the total solid of this composition, as for the total content of a polymerization initiator, 1-40 mass% is more preferable, and 1.5-30 mass% is still more preferable.

In the photopolymerizable composition (2), other known polymerization initiators other than the initiators (1) and (2) may be used in combination as long as the effects of the present invention are not impaired.
Examples of other polymerization initiators include (a) aromatic ketones, (b) aromatic onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, (F) Ketooxime ester compounds, (g) borate compounds, (h) azinium compounds, (i) metallocene compounds, (j) active ester compounds, (k) compounds having a carbon halogen bond, and the like. More specifically, for example, polymerization initiators described in paragraph numbers [0081] to [0139] of JP-A-2006-78749 can be mentioned.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Support]
As the support in the lithographic printing plate precursor according to the invention, a support having a hydrophilic surface is preferable. As the hydrophilic support, a conventionally known hydrophilic support used for a lithographic printing plate can be used without limitation.

In particular, preferable supports include paper, polyester film or aluminum plate, among which dimensional stability is good, relatively inexpensive, and a surface having excellent hydrophilicity and strength is provided by surface treatment as necessary. An aluminum plate which can be used is particularly preferred. A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferable.
The surface of these supports may be subjected to appropriate known physical and chemical treatments for the purpose of imparting hydrophilicity and improving strength, if necessary.

  The composition of the aluminum plate used as the support in the present invention is not specified, and conventionally known and used aluminum plates can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, and particularly preferably 0.2 mm to 0.3 mm.

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

Furthermore, after performing these treatments, the hydrophilization treatment may be performed with a water-soluble resin or silicate.
The hydrophilization treatment is applied to make the surface of the support hydrophilic, in order to prevent harmful reactions of the photopolymerizable composition provided thereon, and to improve the adhesion of the photosensitive layer, etc. It is for the purpose.

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

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

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

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

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

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

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

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

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

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

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

  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, Tables 1 and 2 below show details of polymerization initiators (Compound 1-1 to Compound 2-3) used in Examples and Comparative Examples.

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

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

Subsequently, Compound 1-1 is synthesized using Compound B according to the following scheme.
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 1 having the following structure (yield 19.5 g, yield). 99%).

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

  Other oxime compounds (polymerization initiators) are synthesized in the same manner. Further, Compound 2-1 is available as Irgacure OXE 01 manufactured by Ciba Specialty Chemicals, and Compound 2-2 is available as Irgacure OXE 02. Compound 2-3 was synthesized by the method described in JP-A-2006-36750.

[Example 1-1]
<Preparation of photopolymerizable composition A-1>
The formulation of the following photopolymerizable composition A-1 was uniformly mixed to prepare a photopolymerizable composition A-1 for a color filter.
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 (approximately 4. 51 parts by mass) and 150 parts by mass of ethyl 3-ethoxypropionate as a solvent were mixed and dispersed by a bead mill for 15 hours to prepare a pigment dispersion (P1).

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

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

<Composition A-1>
Pigment dispersion (P1) 600 parts by mass Alkali-soluble resin 200 parts by mass (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, mol ratio: 80/10/10, Mw: 10,000)
Polyfunctional monomer dipentaerythritol hexaacrylate 60 parts by mass Oxime compound 1-1 [Initiator (1)] 55 parts by mass Oxime compound 1-2 [Initiator (2)] 5 parts by mass Solvent: 1000 parts by mass of propylene glycol monomethyl ether acetate, surfactant (trade name: Tetranic 150R1, BASF) 1 part by mass, 5 parts by mass of γ-methacryloxypropyltriethoxysilane

[Example 1-2 to Example 1-19, Comparative Example 1-1 to Comparative Example 1-7]
In Example 1-1, except that the initiator used was changed to the compounds and addition amounts shown in Tables 1 and 2 below, respectively, the photopolymerizable compositions 1-2 to 2 were carried out in exactly the same manner as in Example 1-1. 1-19 and Comparative Examples 1-1 to 1-7 were respectively prepared.

[Examples 1-20 to 1-25]
In Example 1-1, the initiator used was changed to the compounds and addition amounts shown in Table 2 below, and the sensitizers and co-sensitizers shown in Table 2 were added. Photopolymerizable compositions 1-20 to 1-24 were prepared in exactly the same manner. In Example 1-25, 20 parts by mass of Compound 1-3 was further added as a third polymerization initiator.
The sensitizers and co-sensitizers listed in Table 2 below are as shown below.
Sensitizer A1: 4,4-bisdiethylaminobenzophenone sensitizer A2: diethylthioxanthone cosensitizer C1: 2-mercaptobenzimidazole cosensitizer C2: 2-mercaptobenzthiazole cosensitizer C3: N-phenyl 2-Mercaptobenzimidazole

A color filter was produced using the photopolymerizable composition A-1 for forming a color filter.
[2. (Production of color filter)
2-1. Formation of a photopolymerizable composition layer The photopolymerizable composition A-1 containing a 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 as it was for 10 minutes. And then subjected to vacuum drying and prebaking (100 ° C., 80 seconds) to form a photopolymerizable composition coating film (photopolymerizable composition layer).

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

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

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

[3. (Performance evaluation)
Storage stability and exposure sensitivity of a colored photopolymerizable composition, developability when a colored pattern is formed on a glass substrate using the colored photopolymerizable composition, coloring of the obtained colored pattern over time, substrate The adhesion and pattern cross-sectional shape were evaluated as follows. The evaluation results are collectively shown in Table 1 and Table 2 below.

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

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

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

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

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

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

<Pattern cross-sectional shape>
The cross-sectional shape of the formed pattern was observed and evaluated. The cross-sectional shape of the pattern is most preferably a forward taper, and a rectangular shape is next preferred. Reverse taper is not preferred.
<Surface smoothness>
Slit coating suitability was evaluated using a slit coating apparatus equipped with a slit head having a slit interval of 100 μm and a coating effective width of 500 mm. After coating on 10 glass substrates (width 550 mm, length 650 mm, thickness 0.7 mm) by a usual method, the slit head was kept in the air for 5 minutes and forcedly dried. After waiting, a dummy dispensing was performed for 3 seconds, and 10 slits were applied to the glass substrate intermittently. The interval between the slit and the glass substrate was adjusted so that the coating thickness after post-baking was 2 μm, and the curable composition was applied at a coating speed of 100 mm / second. After the application, the sample was pre-baked on a hot plate at 90 ° C. for 60 seconds, and then the number of streaky irregularities on the coated surface was visually counted using a sodium light source and evaluated according to the following criteria.
-Evaluation criteria-
○: No streak-like unevenness on the coated surface. Δ: 1-5 streaky unevennesses observed. X: 6 or more streaky unevennesses observed.

  From the results of Tables 1 and 2, it can be seen that the colored photopolymerizable composition for a color filter of the present invention is excellent in storage stability (time stability). In addition, these colored photopolymerizable compositions have improved exposure sensitivity compared to the comparative examples, good developability when the colored pattern of the color filter is used for formation, and the resulting colored pattern is heated over time. It can be seen that the surface of the colored pattern is more excellent while maintaining the substrate adhesion of the formed colored pattern and the pattern cross-sectional shape.

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

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

-Coating solution composition for photosensitive layer-
-Polymerizable compound (compound described in Tables 3 and 4 below) 0.80 parts by mass-Binder polymer (compound described in Tables 3 and 4 below) 0.90 parts by mass-Sensitizer (in Tables 3 and 4 below) Description compound) No addition, or 0.10 parts by mass of initiator (1) (compound described in Tables 3 and 4 below) (Amount described in Tables 3 and 4 below)
Initiator (2) (compound described in Tables 3 and 4 below) (Amount described in Tables 3 and 4 below)
-Co-sensitizer (compound described in Tables 3 and 4 below) No addition or 0.25 parts by mass-0.02 part by mass of fluorosurfactant (Megafac F-177: Dainippon Ink & Chemicals, Inc. ) Made)
-Thermal polymerization inhibitor 0.03 parts by mass (N-nitrosohydroxylamine aluminum salt)
-Ε-type copper phthalocyanine dispersion 0.2 parts by mass-Methyl ethyl ketone 16.0 parts by mass-Propylene glycol monomethyl ether 16.0 parts by mass

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

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

[2. (Lithographic printing plate making)
<Plate making>
The following exposure and development processes were performed on the lithographic printing plate precursor.

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

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

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

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

[3. Performance evaluation]
The sensitivity and storage stability of the lithographic printing plate precursor were evaluated by the following methods. The results are collectively shown in Tables 3 and 4.

(3-1. Evaluation of sensitivity)
The lithographic printing plate precursor is exposed under the above conditions, and immediately after that, developed under the above conditions to form an image. At that time, the area percentage of 50% halftone dots is a halftone dot area measuring device (Gretag-Macbeth). Measured with The larger the number, the higher the sensitivity.

(3-2. Image section printing durability test)
Printing was performed using a lithographic printing plate precursor using “R201” manufactured by Roland as a printing machine and “GEOS-G (N)” manufactured by Dainippon Ink & Chemicals, Inc. as an ink. The printed matter in the solid image portion was observed, and the printing durability was examined based on the number of sheets on which the image began to fade. The higher the number, the better the printing durability.

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

(3-4. Evaluation of surface smoothness)
Slit coating suitability was evaluated using a slit coating apparatus equipped with a slit head having a slit interval of 100 μm and a coating effective width of 500 mm. After coating on 10 aluminum substrates (width 550 mm, length 650 mm, thickness 0.3 mm) by a usual method, the slit head was kept in the air for 5 minutes and forcedly dried. After waiting, a dummy dispensing was performed for 3 seconds, and 10 slits were applied to the aluminum substrate intermittently. The spacing between the slit and the aluminum substrate was adjusted so that the coating thickness after post-baking was 2 μm, and the curable composition was applied at a coating speed of 100 mm / second. After the application, after prebaking at 90 ° C. for 60 seconds with a hot plate, the number of streaky irregularities on the coated surface was visually counted using a sodium light source and evaluated according to the following criteria.
-Evaluation criteria-
○: No streak-like unevenness on the coated surface. Δ: 1-5 streaky unevennesses observed. X: 6 or more streaky unevennesses observed.

  The structures of the polymerizable compounds M, N, and O and the binder polymers B1 and B2 described in Tables 3 and 4 are shown below.

  As is apparent from Tables 3 and 4, the planographic printing plate precursors of Examples 2-1 to 2-10 containing the photopolymerizable composition of the present invention in the photosensitive layer can be patterned with high sensitivity. It can be seen that the stability over time is good, and the smoothness and printing durability of the coating film are improved as compared with the comparative example.

Claims (11)

A photopolymerizable composition comprising: a photopolymerization initiator represented by the following general formula (1); and a photopolymerization initiator represented by the following general formula (2).

[In formula ^{(1), B 1, R} 1 and ^{X 1} each independently represent a monovalent substituent, A represents a divalent organic group, Ar ¹ represents an aryl group. n is an integer of 0-5.
In the general formula (2), B ² and X ² each independently represent a monovalent substituent. Y represents a monovalent substituent including a partial structure having a polymerization initiating ability. m is an integer of 0-5. ]
The photopolymerizable composition according to claim 1, wherein the photopolymerization start represented by the general formula (2) is a compound represented by the following general formula (3).

[In the above general formula (3), B ² , R ^2, X ² and Z each independently represent a monovalent substituent. m is an integer of 0-5. ] The photopolymerizable composition according to claim 2, wherein the photopolymerization start represented by the general formula (3) is a compound represented by the following general formula (4).

[In the general formula (4), B ² , R ² and X ² each independently represent a monovalent substituent, E represents a divalent organic group, and Ar ² represents an aryl group. m is an integer of 0-5. ]   Furthermore, the photoheavy composition of any one of Claim 1 to 3 containing (B) polymeric compound.   Furthermore, (C) The photopolymerizable composition of Claim 4 containing a coloring agent.   The photopolymerizable composition according to claim 5, wherein the (C) colorant is a pigment and further contains (D) a pigment dispersant.   The photopolymerizable composition for color filters containing the photopolymerizable composition of any one of Claim 5 or Claim 6.   The color filter which has a coloring pattern which uses the photopolymerizable composition for color filters of Claim 7 on a support body. Applying a photopolymerizable composition for a color filter according to claim 7 on a support to form a photopolymerizable composition layer;
Pattern exposing the photopolymerizable composition layer;
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 8.   A lithographic printing plate precursor comprising a photosensitive layer containing the photopolymerizable composition according to claim 4 on a support.