JP2006276512A - Photosetting image recording material, and, color filter and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosetting image recording material having high sensitivity and giving high rectangularity of a pattern shape and a color filter using the same, and to provide a method for manufacturing the color filter with a high cost performance. <P>SOLUTION: The photosetting image recording material has on a support a photopolymerizable layer containing a xanthene dye having an absorption maximum at 500-600 nm wavelength, a pyrazolone azo dye having an absorption maximum at 400-550 nm wavelength and a radical polymerizable monomer and a layer containing polyvinyl alcohol, in this order. The color filter and a method for manufacturing the photosetting image recording material are also disclosed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photocurable image recording material suitable for forming a colored image constituting a color filter used for a liquid crystal display element (LCD), a solid-state imaging element (CCD, CMOS, etc.), and a photocurable image recording material. The present invention relates to a color filter using the above and a manufacturing method thereof.

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

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

  When producing a color filter by the pigment dispersion method, a radiation sensitive composition is applied on a glass substrate by a spin coater or a roll coater and dried to form a coating film, and the coating film is subjected to pattern exposure and development. A colored pixel is formed by repeating this operation for each color.

  Here, examples of the pigment dispersion method include negative photosensitive compositions in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin (see, for example, Patent Documents 1 to 4). It is known that in these compositions that cure the film by photopolymerization, polymerization inhibition occurs due to oxygen in the environmental atmosphere.

  In recent years, there has been a demand for higher definition in color filters for solid-state imaging devices. However, it is difficult to further improve the resolution with conventional pigment dispersion systems, and there are problems such as color unevenness caused by coarse particles of the pigment, so that it is used for applications that require fine patterns such as solid-state imaging devices. Was not suitable.

  In order to deal with such a problem, a technique for using a dye instead of a pigment has been proposed (see, for example, Patent Documents 5 to 9). However, the dye-containing curable composition has a problem that it is generally inferior to the pigment in various performances such as light resistance, heat resistance, solubility, and coating uniformity. In particular, in the case of the use for producing a color filter for a solid-state image sensor, a film thickness of 1.5 μm or less is required. In the photopolymerizable curable composition to be contained, there was a problem that the polymerization reaction was inhibited, the sensitivity was low, the curing was insufficient, and the adhesion with the substrate was insufficient. Further, when other filter layers, intermediate layers, and the like are laminated in a state where curing is insufficient, there is a concern that the dye may move to other layers even in the cured portion.

JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 5-273411 JP-A-7-140654 JP-A-6-75375 Japanese Patent Laid-Open No. 2002-14220 JP 2002-14221 A Japanese Patent Laid-Open No. 2002-14222 JP 2002-14223 A

  An object of the present invention is to provide a photocurable image-recording material having high sensitivity and a highly rectangular pattern shape, and a color filter using the same. It is another object of the present invention to provide a color filter manufacturing method with high cost performance.

Specific means for solving the above problems are as follows.
<1> On a support, a photopolymerizable layer containing a xanthene dye having an absorption maximum at a wavelength of 500 to 600 nm, a pyrazolone azo dye having an absorption maximum at a wavelength of 400 to 550 nm, and a radical polymerizable monomer, and polyvinyl alcohol A photo-curable image-recording material comprising:

  <2> The photocurable image recording material according to <1>, wherein the photopolymerizable layer contains an oxime photopolymerization initiator.

  <3> A color filter comprising the photocurable image recording material according to <1> or <2>.

  <4> On the support, a colored layer containing a xanthene dye having an absorption maximum at a wavelength of 500 to 600 nm and a pyrazolone azo dye having an absorption maximum at a wavelength of 400 to 550 nm, and a layer containing polyvinyl alcohol in this order. It is a color filter characterized by having.

  <5> A dye-containing curable composition comprising a xanthene dye having an absorption maximum at a wavelength of 500 to 600 nm, a pyrazolone azo dye having an absorption maximum at a wavelength of 400 to 550 nm, and a radical polymerizable monomer on a support. And then applying a polyvinyl alcohol aqueous solution, then exposing through a mask and developing to form a pattern.

  <6> including a step of exposing the surface on which the photopolymerizable layer of the photocurable image recording material according to <1> or <2> is provided through a mask, and developing to form a pattern. This is a method for producing a color filter.

  The method for producing the color filter may include a step of curing the pattern by heating and / or exposure as necessary, or may repeat these steps a plurality of times. Further, the dye may be changed to form a plurality of types of color filters.

  <7> A color filter array including the color filter according to <3> or <4>.

  <8> The photopolymerizability in which the color filter array of <7> further includes a copper phthalocyanine dye having an absorption maximum at a wavelength of 600 to 700 nm, a pyridone azo dye having an absorption maximum at a wavelength of 400 to 500 nm, and a radical polymerizable monomer. A color filter array having a colored layer obtained from the layer.

  <9> A colored layer obtained from the photopolymerizable layer, wherein the color filter array of <7> or <8> further includes a triarylmethane dye having a maximum absorption at a wavelength of 550 to 650 nm and a radical polymerizable monomer. A color filter array.

  <10> The color filter array according to <8> or <9>, wherein the photopolymerizable layer contains an oxime photopolymerization initiator.

  According to the present invention, it is possible to provide a photocurable image recording material having high sensitivity and excellent pattern shape rectangularity, a color filter using the same, and a method for producing the same.

<< Photocurable image recording material >>
The photocurable image-recording material of the present invention comprises a support, a support, a xanthene dye having an absorption maximum at a wavelength of 500 to 600 nm, a pyrazolone azo dye having an absorption maximum at a wavelength of 400 to 550 nm, and radical polymerization. It has a photopolymerizable layer containing a polymerizable monomer and a layer containing polyvinyl alcohol in this order. According to the present invention, pattern rectangularity can be improved by using a specific dye. In addition, according to the photocurable image recording material of the present invention, a layer containing polyvinyl alcohol (hereinafter sometimes referred to as “PVA layer”) functions as a gas barrier layer, and oxygen that inhibits the polymerization reaction is light. Intrusion into the polymerizable layer can be prevented. Thereby, it is estimated that the polymerizability of a photopolymerizable layer increases and the rectangularity of a pattern improves further. Moreover, since the polymerization reaction of the photopolymerizable layer is not inhibited by oxygen, the sensitivity can be improved at the same time.

  The photopolymerizable layer in the present invention preferably contains an oxime photopolymerizable initiator. By adding to a highly sensitive oxime photoinitiator, the sensitivity improvement by the above-mentioned PVA layer can be made more excellent.

  In the present invention, the color filter (red) of the present invention can be obtained by exposing and developing the photopolymerizable layer of the photocurable image forming material of the present invention. Moreover, in this invention, a color filter array can be produced by combining the color filter of this invention with the colored layer of another color (green, blue).

<Photopolymerizable layer>
The photopolymerizable layer includes a xanthene dye having an absorption maximum at least at a wavelength of 500 to 600 nm (hereinafter sometimes simply referred to as “xanthene dye”), a pyrazolone azo dye having an absorption maximum at a wavelength of 400 to 550 nm ( Hereinafter, it is simply referred to as a “pyrazolone azo dye”) and a layer containing a radical polymerizable monomer, and is configured to contain an alkali-soluble resin, a photopolymerization initiator, or the like, if necessary.
The thickness of the photopolymerizable layer in the present invention is preferably from 0.1 μm to 10 μm, more preferably from 0.4 μm to 3 μm, from the viewpoint of forming a cured film by photopolymerization.

The photopolymerizable layer in the present invention can be formed by applying and drying a dye-containing curable composition on a support. For example, in the case of forming a negative photopolymerizable layer in the present invention, the dye-containing curable composition contains the xanthene dye, the pyrazolone azo dye, and the polymerizable compound, and is further necessary. Depending on the case, it comprises an alkali-soluble resin, a photopolymerization initiator, a crosslinking agent, an organic solvent, a dispersant and the like.
In addition, each addition amount in the said dye-containing curable composition can be suitably determined so that it may become a preferable addition amount in the photopolymerizable layer in this invention.

(dye)
-Red dye-
The photopolymerizable layer in the present invention includes at least a xanthene dye having an absorption maximum at a wavelength of 500 to 600 nm (hereinafter sometimes referred to as “pigment (I)”) and a pyrazolone having an absorption maximum at a wavelength of 400 to 550 nm. Azo dyes (hereinafter sometimes referred to as “pigment (II)”). Hereinafter, the photopolymerizable layer containing the xanthene dye and pyrazolone azo dye in the present invention may be referred to as a “red photopolymerizable layer”, and a layer obtained by photopolymerizing the red photopolymerizable layer is referred to as a “red filter layer”. There is a case.

  Examples of the xanthene dye (pigment (I)) having an absorption maximum at a wavelength of 500 to 600 nm contained in the photopolymerizable layer in the invention include a compound represented by the following general formula (I) or a salt thereof.

〔式中、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²およびＲ¹³は、それぞれ独立して水素原子または炭素数１〜３のアルキル基を示し、Ｒ¹⁴、Ｒ¹⁵およびＲ¹⁶はそれぞれ独立してスルホン酸基若しくはその塩、スルホンアミド基または下記一般式（１）で示される置換スルファモイル基を示す。〕

[Wherein R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a sulfonic acid. Group or a salt thereof, a sulfonamide group, or a substituted sulfamoyl group represented by the following general formula (1). ]

R ¹⁷ HNSO ₂ -general formula (1)
[In the formula, R ¹⁷ represents an alkyl group having 2 to 20 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain, and 2 to 12 carbon atoms. An alkyl group having 2 to 12 carbon atoms substituted by an alkoxyl group, a phenyl group substituted by an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms substituted by a phenyl group; -1) represents an alkylcarboxylalkyl group, and an alkyloxycarbonylalkyl group represented by the following general formula (1-2). ]

R ¹⁸⁰ —CO—O—R ¹⁸¹ — General formula (1-1)
[Wherein R ¹⁸⁰ represents an alkyl group having 2 to 12 carbon atoms, and R ¹⁸¹ represents an alkylene group having 2 to 12 carbon atoms. ]

R ¹⁹⁰ —O—CO—R ¹⁹¹ — General formula (1-2)
[Wherein R ¹⁹⁰ represents an alkyl group having 2 to 12 carbon atoms, and R ¹⁹¹ represents an alkylene group having 2 to 12 carbon atoms. ]

Examples of the alkyl group having 1 to 3 carbon atoms represented by R ¹⁰ , R ¹¹ , R ¹² and R ¹³ in the compound represented by the general formula (I) include a methyl group, an ethyl group and a propyl group. .

The sulfonic acid group represented by R ¹⁴ , R ¹⁵ and R ¹⁶ in the compound represented by the general formula (I) may be unsubstituted or may have a substituent.
In the substituted sulfamoyl group represented by the general formula (1) of R ¹⁴ , R ¹⁵ and R ¹⁶ , examples of the alkyl group having 2 to 20 carbon atoms in R ¹⁷ include an ethyl group, a propyl group, an n-hexyl group, n-nonyl group, n-decyl group, n-dodecyl group, 2-ethylhexyl group, 1,3-dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, 1,1,3,3-tetra A methylbutyl group etc. are mentioned.
Examples of the cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain in R ¹⁷ include a cyclohexylethyl group, a 3-cyclohexylpropyl group, and an 8-cyclohexyloctyl group. Examples of the alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain include 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2- (n-butyl) cyclohexyl group and the like.

Examples of the alkyl group having 2 to 12 carbon atoms substituted with an alkoxyl group having 2 to 12 carbon atoms in R ¹⁷ include, for example, 3-ethoxy-n-propyl group, propoxypropyl group, 4-propoxy-n-butyl group. , 3-methyl-n-hexyloxyethyl group, 3- (2-ethylhexyloxy) propyl group and the like.
As the phenyl group substituted with an alkyl group having 1 to 20 carbon atoms in the R ^17, for example, such as o- isopropylphenyl group. Moreover, as a C1-C20 alkyl group substituted by the phenyl group, a benzyl group, 3-phenyl- n-butyl group etc. are mentioned, for example.

Examples of the alkyl group having 2 to 12 carbon atoms represented by R ¹⁸⁰ and R ¹⁹⁰ in the general formula (1-1) and the general formula (1-2) include, for example, an ethyl group, a propyl group, an n-hexyl group, n-nonyl group, n-decyl group, n-dodecyl group, 2-ethylhexyl group, 1,3-dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, 1,1,3,3-tetra A methylbutyl group etc. are mentioned.
Examples of the alkylene group having 2 to 12 carbon atoms represented by R ¹⁸¹ and R ¹⁹¹ in the general formula (1-1) and the general formula (1-2) include a dimethylene group, a trimethylene group, and a tetramethylene group. , Pentamethylene group, hexamethylene group and the like.

The xanthene dye in the present invention may be a compound represented by the general formula (I) or a salt of the compound represented by the general formula (I). Examples of such salts include alkali metal salts with alkali metals such as sodium and potassium; amines such as triethylamine and 1-amino-3-phenylbutane. Such a salt forms a salt with the sulfonic acid group when the substituents R ¹⁴ , R ¹⁵ and R ^{16 of the} compound represented by the general formula (I) are sulfonic acid groups.

  As the xanthene dye in the present invention, for example, the compound represented by the general formula (I) or a salt thereof may be used alone, or two or more kinds thereof may be mixed and used. Specific examples of xanthene dyes in the present invention include C.I. Acid Red 289.

  Examples of the pyrazolone azo dye (pigment (II)) having an absorption maximum at a wavelength of 400 to 550 nm contained in the photopolymerizable layer in the present invention include compounds represented by the following general formula (II) and salts thereof.

〔式中、Ｒ²¹およびＲ²²はヒドロキシル基またはカルボン酸基を示し、Ｒ²⁰、Ｒ²³、Ｒ²⁴およびＲ²⁵は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜４のアルキル基、スルホン酸基、炭素数１〜４のアルコキシル基またはニトロ基を示す。〕

[Wherein R ²¹ and R ²² represent a hydroxyl group or a carboxylic acid group, and R ²⁰ , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a halogen atom, or an alkyl having 1 to 4 carbon atoms. Group, a sulfonic acid group, an alkoxyl group having 1 to 4 carbon atoms or a nitro group. ]

The carboxylic acid group represented by R ²¹ or R ²² in the compound represented by the general formula (II) may be unsubstituted or may have a substituent.

Examples of the halogen atom represented by R ²⁰ , R ²³ , R ²⁴ and R ²⁵ in the compound represented by the general formula (II) include a fluorine atom, a chlorine atom and a bromine atom.
Moreover, as a C1-C4 alkyl group in said R <^20> , R <^23> , R < ²⁴ >, R < ²⁵ >, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned, for example.
In the compound represented by the general formula (II), R ²⁰ , R ²³ , R ²⁴ and R ²⁵ and the sulfonic acid group represented by R ²¹ and R ²² may be unsubstituted or have a substituent. May be.

Examples of the alkoxyl group having 1 to 4 carbon atoms in R ²⁰ , R ²³ , R ²⁴ and R ²⁵ include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

The pyrazolone azo dye in the present invention may be, for example, a compound represented by the general formula (II) or a salt of the compound. Examples of the salt include alkali metal salts with alkali metals such as sodium and potassium; amine salts with amines such as triethylamine, 2-ethylhexylamine and 1-amino-3-phenylbutane. Such a salt is usually a salt of the sulfonic acid group when at least one substituent of R ²³ , R ²⁴ , R ²⁵ and R ²⁶ of the compound represented by the general formula (II) is a sulfonic acid group. Is formed.
The compound represented by the general formula (II) may be coordinated to a chromium atom to form a complex. The compound represented by the general formula (II) can further improve the light resistance of the red filter layer by forming a complex with a chromium atom.

  Examples of the pyrazolone azo dyes in the present invention include C.I. Acid Yellow 17 (C.I. Acid Yellow 17), C.I. Solvent Orange 56, and C.I. -Solvent yellow 82 (CI Solvent Yellow 82) etc. are mentioned, These may each be used independently and may be used in mixture of 2 or more types.

The content of the xanthene dye and pyrazolone azo dye in the present invention contained in the photopolymerizable layer in the present invention is such that the transmittance of the photopolymerizable layer in the present invention is 1% or less at a wavelength of 535 nm and 90% at a wavelength of 650 nm. It is preferable to adjust so that it may become above. Specifically, the contents of the xanthene dye and pyrazolone azo dye in the present invention in the photopolymerizable layer in the present invention are 15 to 85% by mass with respect to the total solid content (mass) from the viewpoint of spectral characteristics. It is preferable that it is 30-80 mass%. In addition, the content of each of the xanthene dye and the pyrazolone azo dye in the present invention is usually 20 to 60 masses when the total amount of all the dyes is 100 parts by mass. It is preferably about part, and more preferably 30 to 50 parts by mass. In addition, the content of the pyrazolone azo dye is usually preferably about 80 to 40 parts by mass, and more preferably 70 to 50 parts by mass.
When the content of the xanthene dye is in the range of 20 to 60 parts by mass, the light resistance of the red filter layer can be sufficiently improved, and the spectral characteristics with respect to red light are prevented from becoming insufficient. be able to. In addition, when the content of the pyrazolone azo dye is in the range of 40 to 80 parts by mass, the light resistance of the red filter layer can be sufficiently improved, and the spectral characteristics with respect to red light are insufficient. In addition to preventing i-line absorption of the red photopolymerizable layer, it is possible to prevent the pattern from being difficult to form by exposure.

  The photopolymerizable layer (red photopolymerizable layer) in the present invention may contain other dyes for the purpose of toning, that is, adjustment of spectral characteristics, and has, for example, an absorption maximum at a wavelength of 400 to 500 nm. It may contain a pyridone azo dye (hereinafter sometimes referred to as “dye (III)”).

  Examples of the dye (III) include compounds represented by the following general formula (III). By including the compound represented by the following general formula (III) in the photopolymerizable layer in the present invention, the spectral characteristics of the red filter layer can be further improved, and the transmittance can be 5% or less at a wavelength of 450 nm.

〔式中、Ｒ³⁰は炭素数２〜１０のアルキル基を示す。Ｒ³¹、Ｒ³²、Ｒ³⁴はそれぞれ独立して水素原子、メチル基、ヒドロキシル基またはシアノ基を示す。Ｒ³³は炭素数１〜４のアルキル基を示す。〕

[Wherein R ³⁰ represents an alkyl group having 2 to 10 carbon atoms. R ³¹ , R ³² and R ³⁴ each independently represent a hydrogen atom, a methyl group, a hydroxyl group or a cyano group. R ³³ represents an alkyl group having 1 to 4 carbon atoms. ]

In the compound represented by the general formula (III), examples of the alkyl group having 2 to 10 carbon atoms represented by R ³⁰ include an ethyl group, a propyl group, an n-hexyl group, an n-nonyl group, an n-decyl group, Examples include n-dodecyl group, 2-ethylhexyl group, 1,3-dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, 1,1,3,3-tetramethylbutyl group. The alkyl group having 1 to 4 carbon atoms represented by R ^33, for example, a methyl group, an ethyl group, a propyl group, a butyl group.

  As the dye (III), a compound represented by the general formula (III) may be used alone, or two or more kinds may be used in combination. Examples of the dye (III) include C.I. Solvent Yellow 162 (CI Solvent Yellow 162).

  When using the said pigment | dye (III), content of the pigment | dye (III) in a red photopolymerizable layer is 10 with respect to 100 mass parts of total amounts of content of pigment | dye (I), and content of pigment | dye (II). -40 mass parts is preferable, and 15-35 mass parts is more preferable. When the content of the dye (III) is in the range of 10 to 40 parts by mass, it is possible to prevent the spectral characteristics with respect to red light from becoming insufficient.

  The transmittance of the photopolymerizable layer (red filter layer) in the present invention after patterning is preferably 1% or less at a wavelength of 535 nm, preferably 90% or more at a wavelength of 650 nm, and more preferably 5% or less at a wavelength of 450 nm. preferable.

  In addition, in the color filter array having a color filter formed using the photocurable image recording material of the present invention, other colored layers (colored filter layers) other than the above-described red filter layer are formed on a support. Can do. In this case, the dye-containing curable composition obtained by changing the dye in the present invention to a dye corresponding to each color described later is applied onto the support on which the red filter layer is formed using the photocurable image recording material in the present invention. It is preferable to form another colored layer (colored filter layer) by drying to form a green or blue photopolymerizable layer and exposing and developing it. The dyes contained in the other colored layers can be appropriately selected from known dyes for conventional color filters. However, xanthene dyes, pyrazolone azo dyes, pyridone azo dyes, triarylmethane dyes and copper phthalocyanine. It is preferable to select the dye according to the desired spectral characteristics.

-Other dyes-
The color filter array having a color filter formed using the photocurable image forming material of the present invention preferably has a combination of color filters (filter layers) of each color. For example, a color filter having a xanthene dye having an absorption maximum at a wavelength of 500 to 600 nm and a pyrazolone azo dye having an absorption maximum at a wavelength of 400 to 550 nm as a red hue, and a wavelength of 600 to 700 nm as a green hue. A colored layer (green filter layer) having a copper phthalocyanine dye having an absorption maximum at 400 nm and a pyridone azo dye having an absorption maximum at a wavelength of 400 to 500 nm, and triallyl having an absorption maximum at a wavelength of 550 to 650 nm as a blue hue It is preferable to combine a colored layer (blue filter layer) having a methane dye.

As described above, the green filter layer includes a copper phthalocyanine dye having an absorption maximum at a wavelength of 600 to 700 nm (hereinafter sometimes referred to as “pigment (VI)”) and a pyridone azo having an absorption maximum at a wavelength of 400 to 500 nm. It is preferable to contain a system dye (hereinafter sometimes referred to as “pigment (V)”).
The green filter layer is preferably formed using a photopolymerizable layer containing at least a radical polymerizable monomer in addition to the dye (VI) and the dye (V).

  Specific examples of the dye (IV) include compounds represented by the following general formula (IV).

〔式中、Ｒ⁴⁰、Ｒ⁴¹、Ｒ⁴²、Ｒ⁴³はそれぞれ独立してスルホン酸基若しくはその塩基、スルホンアミド基または前記一般式（１）で示される置換スルファモイル基を示す。ｉ、ｊ、ｋ、ｍはそれぞれ独立して０〜２の整数を示す。ただし、ｉ＋ｊ＋ｋ＋ｍ≦４である。〕

[Wherein, R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ each independently represent a sulfonic acid group or a base thereof, a sulfonamide group or a substituted sulfamoyl group represented by the general formula (1). i, j, k, and m each independently represent an integer of 0 to 2. However, i + j + k + m ≦ 4. ]

The sulfonic acid groups represented by R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ in the compound represented by the general formula (IV) may be unsubstituted or may have a substituent.

  Examples of the dye (IV) include C.I. Solvent Blue 25 (C.I. Solvent Blue 25), C.I. Solvent Blue 55 (C.I. Solvent Blue 55), and C.I. Solvent Blue 67 (CI Solvent Blue 67), C.I. Acid Blue 249 (C.I. Acid Blue 249), C.I. Direct Blue 86 (C.I. Direct Blue 86), etc. Is mentioned. These may be used alone or in combination of two or more. These pigments (IV) are dyes having an absorption maximum at a wavelength of 600 to 700 nm.

  Examples of the dye (V) include compounds represented by the following general formula (V).

〔式中、Ｒ⁵⁰は炭素数２〜１０のアルキル基を示し、Ｒ⁵¹、Ｒ⁵²、Ｒ⁵⁴はそれぞれ独立して、水素原子、メチル基、ヒドロキシル基またはシアノ基を示し、Ｒ⁵³は炭素数１〜４のアルキル基を示す。〕

[In the formula, R ⁵⁰ represents an alkyl group having 2 to 10 carbon atoms, R ⁵¹ , R ⁵² and R ⁵⁴ each independently represents a hydrogen atom, a methyl group, a hydroxyl group or a cyano group, and R ⁵³ represents a carbon atom. The alkyl group of number 1-4 is shown. ]

In the compound represented by the general formula (V), examples of the alkyl group having 2 to 10 carbon atoms represented by R ⁵⁰ include an ethyl group, a propyl group, an n-hexyl group, an n-nonyl group, an n-decyl group, Examples include n-dodecyl group, 2-ethylhexyl group, 1,3-dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, 1,1,3,3-tetramethylbutyl group. Moreover, as a C1-C4 alkyl group shown by ^R53 , a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned, for example.

  Examples of the dye (V) include C.I. Solvent Yellow 162 (CI Solvent Yellow 162). These pigments (V) are dyes that usually have little i-line absorption and have an absorption maximum at a wavelength of 400 to 500 nm.

  Further, the thickness of the green filter layer and the content of the dye (IV) and the dye (V) in the green filter layer are such that the transmittance of the green filter layer is 5% or less at a wavelength of 450 nm and 62% or more at a wavelength of 535 nm. It is preferable to adjust so. For example, when the thickness of the green filter layer is about 1.6 to 1.9 μm, the total pigment content in the green filter layer is based on the total solid content (mass) from the viewpoint of curability by photopolymerization. 5 to 60% by mass, preferably 10 to 40% by mass. The content of each of the dye (IV) and the dye (V) is, for example, the dye (IV) with respect to 100 parts by mass of the total content of the dye (IV) and the dye (V). When the content of is preferably 30 to 70 parts by mass, more preferably 40 to 50 parts by mass, the transmittance of the green filter layer can be 5% or less at a wavelength of 450 nm and 62% or more at a wavelength of 535 nm. . In this case, the content of the dye (V) is preferably about 70 to 30 parts by mass, and more preferably 60 to 50 parts by mass.

The green filter layer may contain other dyes for the purpose of improving light resistance, toning, that is, adjusting the spectral characteristics. For example, a pyrazolone azo dye having an absorption maximum at a wavelength of 400 to 500 nm (hereinafter, “ May be referred to as “dye (VI)”. By containing such a dye (VI), the light resistance of the green filter layer can be further improved.
Examples of the dye (VI) include a compound represented by the following general formula (VI) or a salt thereof.

〔式中、Ｒ⁶¹、Ｒ⁶²はヒドロキシル基またはカルボン酸基を示し、Ｒ⁶⁰、Ｒ⁶³、Ｒ⁶⁴、Ｒ⁶⁵は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜４のアルキル基、スルホン酸基、炭素数１〜４のアルコキシル基またはニトロ基を示す。〕

[Wherein, R ⁶¹ and R ^{62 each} represent a hydroxyl group or a carboxylic acid group, and R ⁶⁰ , R ⁶³ , R ⁶⁴ and R ⁶⁵ each independently represent a hydrogen atom, a halogen atom, or an alkyl having 1 to 4 carbon atoms. Group, a sulfonic acid group, an alkoxyl group having 1 to 4 carbon atoms or a nitro group. ]

The carboxylic acid group represented by R ⁶¹ or R ⁶² in the compound represented by the general formula (VI) may be unsubstituted or may have a substituent.

Examples of the halogen atom represented by R ⁶⁰ , R ⁶³ , R ⁶⁴ , R ⁶⁵ in the compound represented by the general formula (VI) include a fluorine atom, a chlorine atom, a bromine atom and the like. Moreover, as a C1-C4 alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned, for example. Furthermore, as a C1-C4 alkoxyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, for example.
The sulfonic acid group represented by R ⁶⁰ , R ⁶³ , R ⁶⁴ and R ⁶⁵ in the compound represented by the general formula (VI) may be unsubstituted or may have a substituent.

The dye (VI) may be a compound represented by the general formula (VI) or a salt of the compound. Examples of the salt include alkali metal salts with alkali metals such as sodium and potassium; amine salts with amines such as triethylamine, 2-ethylhexylamine and 1-amino-3-phenylbutane. Such a salt usually has a sulfonic acid group when at least one substituent of R ⁶⁰ , R ⁶³ , R ⁶⁴ and R ⁶⁵ of the compound represented by the general formula (VI) is a sulfonic acid group. A salt is formed. Such a dye (VI) may be coordinated to a chromium atom to form a complex. The dye (VI) can further improve the light resistance of the green filter layer by forming a complex with a chromium atom.

  Examples of the dye (VI) include C.I. Acid Yellow 17 (C.I. Acid Yellow 17), C.I. Solvent Orange 56 (C.I. Solvent Orange 56), and C.I. Solvent yellow 82 (CI Solvent Yellow 82) etc. are mentioned, These may be used independently, respectively, and 2 or more types may be mixed and used for them. These pigments (VI) are dyes having an absorption maximum at a wavelength of 400 to 500 nm.

When the pigment (VI) is used in the green filter layer, the content is usually 70 parts by mass or less with respect to 100 parts by mass in total of the content of the pigment (IV) and the content of the pigment (V). Preferably, it is more preferably 65 parts by mass or less. When the content of the dye (VI) is 70 parts by mass or less, it is possible to prevent the absorption of i-line and the like from becoming so large that it is difficult to form a pattern by exposure.
The content of the dye (VI) is less than 10 parts by mass, and even if the dye (VI) is contained, the spectral characteristics tend to be insufficiently improved. .

Further, the green filter layer may contain a triallylmethane dye (hereinafter sometimes referred to as “dye (VII)”) having an absorption maximum at a wavelength of 580 to 680 nm. By containing the dye (VII), the transmittance at a wavelength of 650 nm can be easily reduced to 10% or less, and the spectral characteristics can be further improved.
Examples of the dye (VII) include a compound represented by the following general formula (VII-1), a compound represented by the general formula (VII-2), or a salt thereof.

〔式中、Ｒ⁷¹、Ｒ⁷²、Ｒ⁷³、Ｒ⁷⁴は、それぞれ独立して、水素原子、メチル基またはエチル基を示す。Ｒ⁷⁵は下記一般式（７−１）で示される置換基または下記一般式（７−２）で示される置換基を示す。〕

[Wherein, R ⁷¹ , R ⁷² , R ⁷³ and R ⁷⁴ each independently represents a hydrogen atom, a methyl group or an ethyl group. R ⁷⁵ represents a substituent represented by the following general formula (7-1) or a substituent represented by the following general formula (7-2). ]

［式中、Ｒ⁷⁶は水素原子またはアミノ基を示す。Ｒ⁷⁷は水素原子またはヒドロキシル基を示す。］

[Wherein R ⁷⁶ represents a hydrogen atom or an amino group. R ⁷⁷ represents a hydrogen atom or a hydroxyl group. ]

［式中、Ｒ⁷⁸は水素原子またはアミノ基を示す。Ｒ⁷⁹は水素原子またはヒドロキシル基を示す。］

[Wherein R ⁷⁸ represents a hydrogen atom or an amino group. R ⁷⁹ represents a hydrogen atom or a hydroxyl group. ]

〔式中、Ｒ⁷¹⁰、Ｒ⁷¹¹は、それぞれ独立して、水素原子または炭素数１〜３のアルキル基を示す。Ｒ⁷¹²は水素原子またはスルホン酸基を示す。Ｒ⁷¹³は、水素原子、スルホン酸基、カルボン酸基、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基または下記一般式（７１）で示される置換基を示す。〕

[Wherein, R ⁷¹⁰ and R ⁷¹¹ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁷¹² represents a hydrogen atom or a sulfonic acid group. R ⁷¹³ represents a hydrogen atom, a sulfonic acid group, a carboxylic acid group, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or a substituent represented by the following general formula (71). ]

—NR ⁷¹⁴ R ⁷¹⁵ (71)
[Wherein, R ⁷¹⁴ and R ⁷¹⁵ each independently represent a hydrogen atom, a phenyl group, a C 1-3 alkyl group, or a phenyl group substituted with a C 1-3 alkoxyl group at the p-position. ]

In the compound represented by the general formula (VII-2), examples of the alkyl group having 1 to 3 carbon atoms represented by R ⁷¹⁰ , R ⁷¹¹ , R ⁷¹³ , R ⁷¹⁴ , and R ⁷¹⁵ include a methyl group, an ethyl group, and propyl Groups and the like. As the alkoxyl group having 1 to 3 carbon atoms represented by R ^713, e.g., a methoxy group, an ethoxy group, a propoxy group and the like.
Furthermore, in the general formula (71), examples of the phenyl group in which the alkoxy group having 1 to 3 carbon atoms represented by R ⁷¹⁴ and R ⁷¹⁵ is substituted at the p-position include, for example, a p-methoxyphenyl group, a p-ethoxyphenyl group, Examples thereof include a p-propoxyphenyl group.

The dye (VII) may be a compound represented by the general formula (VII-1), a compound represented by the general formula (VII-2), or a general formula (VII-2). The salt of the compound shown by these may be sufficient. Examples of the salt of the compound represented by the general formula (VII-2) include metal salts with alkali metals such as sodium and potassium; amines such as triethylamine, 2-ethylhexylamine and 1-amino-3-phenylbutane; And the amine salt thereof. Such a salt may form a salt with a —SO ₃ — residue, or may form a salt with a sulfonic acid group in R ⁷¹² .

Examples of the compound represented by the general formula (VII-1) as the dye (VII) include C.I. Acid Green 16 and C.I. Acid Blue 108. (CI Acid Blue 108), C.I. Acid Green 50, and the like.
Examples of the compound represented by the general formula (VII-2) or the salt represented by the general formula (VII-2) include C.I. Acid Blue 7 (CI Acid Blue 7). , CI Acid Blue 83 (CI Acid Blue 83), CI Acid Blue 90 (CI Acid Blue 90), CI Solvent Blue 38 (C.I. Solvent Blue 38), C.I. Acid Violet 17 (C.I. Acid Violet 17), C.I. Acid Violet 49, C.I. Acid Violet 49, C.I. Acid Violet 49 I. Acid Green 3), C.I. Acid Green 9), etc. It is below. These pigments (VII) may be used alone or in combination of two or more. The dye (VII) has an absorption maximum at a wavelength of 580 to 680 nm.

  When the dye (VII) is used, the content thereof is preferably adjusted so that the transmittance of the green filter layer is 5% or less at 450 nm, 62% or more at a wavelength of 535 nm, and 10% or less at a wavelength of 650 nm. . Specifically, for example, with respect to a total of 100 parts by mass of the content of the dye (IV) and the content of the dye (V), the content of the dye (VII) is preferably usually 70 parts by mass or less. More preferably, it is 65 parts by mass or less. It can prevent that the transmittance | permeability in 535 nm falls that content of pigment | dye (VII) is 70 mass parts or less. Further, if the content of the dye (VII) is less than 5 parts by mass, the transmittance at 650 nm tends to be 10% or less even if the dye (VII) is included. It is preferable that

The color filter array using the color film of the present invention may have a blue filter layer on a support (substrate).
The blue filter layer preferably contains a dye (VIII) having an absorption maximum at a wavelength of 550 to 650 nm. As said pigment | dye (VIII), the compound shown by the above-mentioned general formula (VII-2) and its salt are mentioned, for example.

The dye (VIII) may be a compound represented by the general formula (VII-2) or a salt of a compound represented by the general formula (VII-2). Examples of such salts include metal salts with alkali metals such as sodium and potassium; amine salts with amines such as triethylamine, 2-ethylhexylamine and 1-amino-3-phenylbutane. Such a salt may form a salt with a —SO ₃ — residue, or may form a salt with a sulfonic acid group in R ⁷¹² .

  Examples of the dye (VIII) include C.I. Acid Blue 7 (C.I. Acid Blue 7), C.I. Acid Blue 83, and C.I. Acid Blue 83. -Blue 90 (CI Acid Blue 90), C.I. Solvent Blue 38 (C.I. Solvent Blue 38), C.I. Acid Violet 17 (C.I. Acid Violet 17), C. -I Acid Violet 49 (CI Acid Violet 49), CI Acid Green 3 (CI Acid Green 3), etc. are mentioned. These pigments (VIII) are dyes having an absorption maximum at a wavelength of 550 to 650 nm, and may be used alone or in combination of two or more.

  When the dye (VIII) is made into a dye-containing curable composition, it dissolves in an organic solvent at a high concentration, so that a blue filter layer having sufficient spectral characteristics can be formed even if the thickness is small. The content of the dye (VIII) in the blue filter layer is adjusted so that the transmittance of the blue filter layer is 70% or more at a wavelength of 450 nm and 5% or less at a length of 650 nm.

  The blue filter layer may contain other dyes for the purpose of improving light resistance, toning, that is, adjusting spectral characteristics, for example, copper phthalocyanine-based having an absorption maximum at a wavelength of 600 to 700 nm. It may contain a dye (hereinafter sometimes referred to as “dye (IX)”). Examples of the dye (IX) include a compound represented by the above general formula (IV) or a salt thereof. By containing the coloring matter (IX), the light resistance of the blue filter layer, that is, the performance that does not cause so-called image sticking due to dye fading in a normal use state can be improved.

The dye (IX) may be a compound represented by the general formula (IV) or a salt of a compound represented by the general formula (IV). Examples of such salts include metal salts with alkali metals such as sodium and potassium; amine salts with amines such as trimethylamine, 2-ethylhexylamine and 1-amino-3-phenylbutane. In the case where R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ are sulfonic acid groups, such salts are preferably formed with the sulfonic acid groups.

  Examples of the dye (IX) include C.I. Solvent Blue 25 (C.I. Solvent Blue 25), C.I. Solvent Blue 55 (C.I. Solvent Blue 55), and C.I. -Blue 67 (C.I. Solvent Blue 67), C.I. Acid Blue 249 (C.I. Acid Blue 249), C.I. Direct Blue 86 (C.I. Direct Blue 86), etc. Can be mentioned. These pigments are dyes having an absorption maximum at a wavelength of 600 to 700 nm, and may be used alone or in combination of two or more.

  When the dye (IX) is used, the content of the dye (IX) in the blue filter layer is adjusted so that the transmittance of the blue filter layer is 70% or more at a wavelength of 450 nm and 5% or less at a wavelength of 650 nm. Is preferred. For example, it is preferable that the content of the dye (VIII) is usually 30 to 70 parts by mass with respect to 100 parts by mass of the total of the content of the dye (VIII) and the content of the dye (IX). Part by mass is more preferable. Moreover, it is preferable that content of pigment | dye (IX) shall be 70-30 mass parts normally, and it is still more preferable to set it as 60-40 mass parts. When the content of the dye (VIII) is in the range of 30 to 70 parts by mass, it is possible to prevent the spectral characteristics with respect to blue light from becoming insufficient and the improvement in light resistance from being insufficient.

  Further, the blue filter layer may contain a xanthene dye having an absorption maximum at a wavelength of 500 to 600 nm (hereinafter sometimes referred to as “dye (X)”). As said pigment | dye (X), the compound shown by the above-mentioned general formula (I) and its salt can be used, for example. By containing such a dye (X), the spectral characteristics of the blue filter layer can be adjusted, and the transmittance can be preferably 15% or less at a wavelength of 535 nm.

  As this pigment | dye (X), C.I. Acid Red 289 (CI Acid Red 289) etc. are mentioned, for example. Such a pigment (X) is a dye having an absorption maximum at a wavelength of 500 to 600 nm. As the dye (X), the compound represented by the general formula (I) may be used alone or in combination of two or more.

  When using the said pigment | dye (X), it is preferable to adjust the content in the blue filter layer so that the transmittance | permeability of a blue filter layer may be 15% or less at wavelength 535 nm, for example. Specifically, it is usually preferably 70 parts by mass or less, and preferably 15 to 50 parts by mass with respect to 100 parts by mass of the total content of the pigment (VIII) and the pigment (IX). Further preferred.

In addition, you may mix and use another dye for the dye-containing curable composition of this invention.
The dye can be used without any particular limitation, and includes conventionally known dyes for color filters. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 And dyes described in JP-A-6-194828. From the viewpoint of the chemical structure of the dye, dyes such as triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, etc. Can be used. Particularly preferred are pyrazole azo dyes, anilinoazo dyes, pyrazolotriazole azo dyes, pyridone azo dyes, anthraquinone dyes and anthrapyridone dyes.

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

-Acid dyes-
The acid dye will be described. The acidic dye is not particularly limited as long as it is a dye having an acidic group such as a sulfonic acid, a carboxylic acid, or a phenolic hydroxyl group, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, curing. It is selected in consideration of all required performances such as interaction with other components in the composition, light resistance, heat resistance and the like.

Hereinafter, specific examples of the acid dye will be given. However, the present invention is not limited to these. For example,
Acid alizarin violet N;
Acid black 1, 2, 24, 48;
Acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
Acid chroma violet K;
Acid Fuchsin;
Acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109;
Acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

Acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
Acid violet 6B, 7, 9, 17, 19;
Acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99; 111,112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251;

Direct Yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141;
Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 256, 257, 259, 260, 268, 274, 275, 293;
Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;
Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Modern Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;
Food Yellow 3;
And derivatives of these dyes.

Among the acid dyes,
Acid black 24;
Acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1;
Acid orange 8, 51, 56, 74, 63, 74;
Acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217,249;
Acid violet 7;
Acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 155, 169, 172, 184, 220, 228, 230, 232, 243;
Acid Green 25;
And the like and derivatives of these dyes are preferred.

  Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38, C.I. I. Solvent Orange 45, Rhodamine B, Rhodamine 110, 2,7-Naphthalenedisulfonic acid, 3-[(5-chloro-2-phenoxyphenyl) hydrazono] -3,4-dihydro-4-oxo-5- [minyl] ulyl , Etc. and derivatives of these dyes can also be suitably used.

(Alkali-soluble resin)
The photopolymerizable layer in the present invention preferably contains an alkali-soluble resin. The alkali-soluble resin in the present invention is not particularly limited as long as it is water-soluble or alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble resin is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

In addition to the above, an acid anhydride added to a polymer having a hydroxyl group, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, Polyvinyl alcohol and the like are also useful as the alkali-soluble resin.
Moreover, you may copolymerize the monomer which has hydrophilic property, As an example, alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, Secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate Branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.

  Other examples of the hydrophilic monomer include a tetrahydrofurfuryl group, phosphoric acid, phosphate ester, quaternary ammonium salt, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salt, morpholinoethyl group, and the like. Useful.

  In order to improve the crosslinking efficiency, a polymerizable group may be included in the side chain, and a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is also useful. Examples of the polymer containing a polymerizable group include KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like. In addition, 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.

  Among these various alkali-soluble resins, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  Examples of the acrylic resin include a copolymer composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, KS resist-106 (Osaka Organic Chemical Industry). (Manufactured by Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), etc.

As the alkali-soluble resin, a polymer having a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 × 10 ⁵ is preferable, a polymer of 2000 to 1 × 10 ⁵ is more preferable, and 5000 to ⁵ is preferable. A polymer of × 10 ⁴ is particularly preferred.

  As content in the photopolymerizable layer in this invention of the said alkali-soluble resin, 10-90 mass% is preferable with respect to the total solid (mass), 20-80 mass% is more preferable, 30-70 mass. % Is particularly preferred.

(Radically polymerizable monomer)
The photopolymerizable layer in the present invention can contain a radical polymerizable monomer. As the radical polymerizable monomer, a compound having at least one addition polymerizable ethylenic double bond and having a boiling point of 100 ° C. or higher under normal pressure is preferable. Further, the radical-polymerizable monomer can be incorporated into a negative-type dye-containing negative curable composition by containing it together with a photopolymerization initiator described later.

  Examples of the radical polymerizable monomer include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate , Trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, hexanediol (meth) acrylate,

Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polymethic alcohol such as glycerin and trimethylolethane, and then (meth) acrylated after adding ethylene oxide or propylene oxide, Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, Mention polyfunctional acrylates and methacrylates such as polyester acrylates, epoxy resins and epoxy acrylates which are reaction products of (meth) acrylic acid described in JP-B 52-30490 and mixtures thereof Can do. Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  The content of the radical polymerizable monomer in the photopolymerizable layer in the present invention is preferably from 0.1 to 90 mass%, more preferably from 1.0 to 80 mass%, based on the total solid content (mass), 2.0-70 mass% is especially preferable.

(Photopolymerization initiator)
The photopolymerizable layer in the present invention preferably contains a photopolymerization initiator. As the photopolymerization initiator, known initiators and initiator systems can be used.
Examples of the photopolymerization initiator include at least one active halogen compound selected from an oxime photopolymerization initiator, a halomethyloxadiazole compound, and a halomethyl-s-triazine compound, a lophine dimer, a benzophenone compound, and acetophenone. Examples thereof include compounds, derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and oxime-based photopolymerization initiators are particularly preferable.
Specifically, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Substituted α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,722,512 Aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367. Triarylimidazole dimer / p-aminophenylketone combination, benzothiazole compound disclosed in Japanese Patent Publication No. 51-48516 / tri And halomethyl-s-triazine compounds.

As the oxime photopolymerization initiator, the oxime photopolymerization initiator may be an oxime photopolymerization initiator described in JP-A-2000-80068, International Publication WO-02 / 100903A1, JP-A-2001-233842, or the like. Are known. When two types of the oxime photopolymerization initiator are selected, compounds having two types of structures can be arbitrarily selected from these known compound groups.
Examples of the oxime-based photopolymerization initiator include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [ 4- (phenylthio) phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O -Benzoyloxime) -1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylpheny Thio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyl) Oxime) -1- [9-ethyl-6- (2-methybenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6 (2-butyl benzoyl) -9H- carbazol-3-yl] ethanone, and the like. However, the present invention is not limited to these.

  Among these, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone (both manufactured by Ciba Specialty Chemicals Co., Ltd.) is preferred in terms of sensitivity.

  Examples of the active halogen compound that is the halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloromethyl, and the like. -5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxy) Styryl) -1,3,4-oxadiazole, and the like.

  Examples of the active halogen compound which is a halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281 and 2- (naphtho-) described in JP-A-53-133428. 1-yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound.

  Specifically, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl) -1 , 3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1-p -Dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6- Bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl)- , 6-Bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -Naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine,

2- [4- (2-Ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5- Methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2 -(5-Methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl -S-triazine, 2- 6-Ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s -Triazine,

4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonyl) Methyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, -Di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine ,

4- [pN- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s- Triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) Minophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine,

4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N- Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-fluoro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-p -N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2, 6-di (trick Romechiru) -s- triazine,

4- [m-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine,

4- (o-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro -PN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) ) -S-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloro) Ethylamino) -2,6-di (trichloromethyl) -s-triazine.

  In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123) manufactured by Midori Chemical Co., Ltd., manufactured by PANCHIM T series (for example, T-OMS, T-BMP, T-R, TB), Irgacure series (for example, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000) manufactured by Ciba Specialty Chemicals Co., Ltd. , Irgacure 149, Irgacure 819, Irgacure 261), Darocur series (eg Darocur 1173), 4,4′-bis (diethylamino) -benzophenone, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2,2- Dimethoxy-2-fu Enylacetophenone, ethanone,

2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2, 4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether, and the like.

A sensitizer and a light stabilizer can be used in combination with these photopolymerization initiators.
Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9. Anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzylacetone, p- (dimethylamino) phenylstyryl ketone, p- ( Dimethylamino) phenyl-p-methyls Rilketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400, etc. Can be mentioned.

  The total amount of the photopolymerization initiator (and known initiator) used is preferably 0.01% by mass to 50% by mass and preferably 1% by mass to 30% with respect to the radical polymerizable monomer solid content (mass). % By mass is more preferable, and 1% by mass to 20% by mass is particularly preferable. When the amount used is in the range of 0.01% by mass to 50% by mass, the polymerization sufficiently proceeds and the film strength can be improved.

(Crosslinking agent)
In the present invention, it is also possible to obtain a film that has been further cured by using a crosslinking agent. Hereinafter, the crosslinking agent will be described.
The crosslinking agent usable in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. At least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with at least one substituent selected from Substituted phenolic compounds, naphthol compounds or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are preferred.

  The epoxy resin (a) may be any epoxy resin as long as it has an epoxy group and has crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. , Hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diphthalic acid diglycidyl ester, N, N-diglycidyl aniline and other divalent glycidyl group-containing low molecular weight compounds, as well as trimethylolpropane triglycidyl ether, Trivalent glycidyl group-containing low molecular weight compounds represented by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc., as well as pentaerythritol tetraglycidyl ether, tetramethylol vinyl Tetravalent glycidyl group-containing low molecular weight compounds typified by phenol A tetraglycidyl ether, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, polyglycidyl ( And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 for melamine compounds, 2 for glycoluril compounds, guanamine compounds, and urea compounds. Although it is -4, Preferably it is 5-6 in the case of a melamine compound, and is 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.
Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of (b) are collectively referred to as a compound (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group) in (b).

  The methylol group-containing compound in (b) can be obtained by heating the alkoxymethyl group-containing compound in (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound in (b) can be obtained by mixing and stirring the methylol group-containing compound in (b) with acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compound in (b) having the substituent will be given.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

  Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol. Examples thereof include compounds obtained by acyloxymethylating 1 to 3 methylol groups of guanamine, or mixtures thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds in which 1 to 3 are acyloxymethylated or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
These compounds in (b) may be used alone or in combination.

  The crosslinking agent (c), that is, a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is the crosslinking agent (b As in the case of), intermixing with the overcoated photoresist is suppressed by thermal crosslinking, and the film strength is further increased. Hereinafter, these compounds may be collectively referred to as a compound (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group) in (c).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinking agent (c) is at least 2 per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

As the methylol group-containing compound in (c), a compound in which the phenolic OH group has a hydrogen atom at the 2-position or 4-position is used as a raw material, and this is used as sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium hydroxide, etc. Obtained by reacting with formalin in the presence of a basic catalyst.
The alkoxymethyl group-containing compound in (c) can be obtained by heating the methylol group-containing compound in (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like.
The acyloxymethyl group-containing compound in (c) can be obtained by reacting the methylol group-containing compound in (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeleton compound in the crosslinking agent (c) include phenol compounds, naphthols, hydroxyanthracene compounds, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. For example, phenol, cresol isomers, 2 , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

  Specific examples of the crosslinking agent (c) include, as a phenol compound, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol- Compounds obtained by methoxymethylating one or two methylol groups of 3-cresol, tri (methoxymethyl) -3-cresol, trimethylol-3-cresol, dimethylol cresol such as 2,6-dimethylol-4-cresol, Compounds obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4 ′ − Suhydroxybiphenyl, TrisP-PA hexamethylol, TrisP-PA hexamethoxymethyl, TrisP-PA hexamethylol compound methoxymethylated from 1 to 5 methylol groups, Bishydroxymethylnaphthalenediol, etc. Is mentioned.

  In addition, examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene, and examples of the acyloxymethyl group-containing compound include, for example, a part of the methylol group of the methylol group-containing compound or Examples include compounds that are all acyloxymethylated.

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds in (c) may be used alone or in combination.

  The total content of the crosslinking agent in the photopolymerizable layer varies depending on the material, but is preferably 1 to 70% by mass, and 5 to 50% by mass with respect to the solid content (mass) of the curable composition. More preferably, 7-30 mass% is especially preferable.

-Thermal polymerization inhibitor-
In addition to the above, it is preferable to add a thermal polymerization inhibitor to the photopolymerizable layer in the present invention. For example, 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), 2-mercaptobenzimidazole, etc. are useful.

(Organic solvent)
When preparing the dye-containing curable composition that can be used for forming the photopolymerizable layer in the present invention, an organic solvent can be used. It is preferable to use a mixture of two or more of these organic solvents. The organic solvent is not particularly limited as long as the solubility of each component and the coating property of the dye-containing curable composition are satisfied, but it is particularly selected in consideration of the solubility, coating property, and safety of the dye and binder. It is preferred that

  Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and methyl lactate. , Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc .;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone are preferred; aromatic hydrocarbons such as toluene and xylene are preferred.

(Various additives)
In the dye-containing curable composition, various additives such as fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc., as necessary Can be blended.

  Specific examples of the various additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic And anionic surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimetoki Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. And an anti-aggregation agent such as sodium polyacrylate.

Further, when the alkali solubility of the non-image area is promoted and the developability of the photopolymerizable layer in the present invention is further improved, the composition contains an organic carboxylic acid, preferably a low molecular weight organic compound having a molecular weight of 1000 or less. Carboxylic acid can be added.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

-Aspect of the photopolymerizable layer-
The photopolymerizable layer in the present invention may be a negative type or a positive type.
The photopolymerizable layer in the present invention is formed using a negative dye-containing curable composition containing the dye, radical polymerizable compound, alkali-soluble resin, photopolymerization initiator, and other crosslinking agent in the present invention described above. However, it can also be formed by using the following dye-containing curable composition.

-Positive type photopolymerizable layer-
When the photopolymerizable layer is a positive type, the dye-containing curable composition used for the photopolymerizable layer can contain, for example, a photosensitive agent and an alkali-soluble resin in addition to the above-described dye.
As the photosensitizer, the same photosensitizer as that used in an ordinary photocurable resin composition can be used. For example, an ester of a phenol compound and an o-naphthoquinonediazide sulfonic acid compound can be used. .

  Examples of the phenol compound include compounds represented by the following general formula (A). Examples of the o-naphthoquinone diazide sulfonic acid compound include o-naphthoxynone diazide-5-sulfonic acid and o-naphthoxynone diazide-4-sulfonic acid.

  The alkali-soluble resin is a resin that can be dissolved in an alkaline developer, and the same alkali-soluble resin as that used in a normal photocurable composition can be used. Examples of the alkali-soluble resin include a novolak resin of p-cresol, a novolak resin of p-cresol and m-cresol, a novolak resin such as a novolak resin having a structure represented by the following general formula (B), polyvinylphenol, Examples include copolymers of styrene and vinylphenol. As the alkali-soluble resin, a novolak resin is preferably used.

  Content of pigment | dye (I) and (II) in the said positive type dye containing curable composition, a photosensitive agent, and alkali-soluble resin is 100 mass parts of total amounts of each pigment | dye, photosensitive agent, and alkali-soluble resin. On the other hand, the total content of the dye is preferably 25 to 55 parts by mass, the content of the photosensitizer is preferably 25 to 55 parts by mass, and the content of the alkali-soluble resin is usually 3 to 50. It is preferable that it is a mass part.

  The positive dye-containing curable composition may contain a curing agent. By containing the curing agent, the mechanical strength of the pattern formed using the positive type dye-containing curable composition can be increased.

  As the curing agent, a heat curing agent that is normally cured by heating can be used. Examples of the heat curing agent include compounds represented by the following general formula (C).

〔式中、Ｑ¹、Ｑ²、Ｑ³、Ｑ⁴は、それぞれ独立して、水素原子、炭素数１〜４のヒドロキシアルキル基または炭素数１〜４のアルコキシル基で置換された炭素数１〜４のアルキル基を示す。Ｚはフェニル基または下記一般式（Ｃ−１）で示される置換基を示す。ただし、Ｑ¹〜Ｑ⁶のうちの少なくとも１つは炭素数１〜４のヒドロキシアルキル基または炭素数１〜４のアルコキシル基で置換された炭素数１〜４のアルキル基である。〕

[Wherein, Q ¹ , Q ² , Q ³ , Q ⁴ are each independently a hydrogen atom, a C 1 -C 4 hydroxyalkyl group or a C 1 -C 4 alkoxyl group substituted with 1 carbon atom. -4 alkyl groups are shown. Z represents a phenyl group or a substituent represented by the following general formula (C-1). However, at least one of Q ^{1 to} Q ^{6 is} a C 1-4 alkyl group substituted with a C 1-4 hydroxyalkyl group or a C 1-4 alkoxyl group. ]

Q ⁵ Q ⁶ N- Formula (C-1)
(In the formula, Q ⁵ and Q ⁶ are each independently a hydrogen atom, a hydroxyalkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms substituted with an alkoxyl group having 1 to 4 carbon atoms. Show.)

  Examples of the hydroxyalkyl group having 1 to 4 carbon atoms in the general formula (C) include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group. Moreover, as a C1-C4 alkyl group substituted by the C1-C4 alkoxyl group, a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a propoxybutyl group is mentioned, for example. Examples of the compound represented by the general formula (C) include hexamethoxymethyl melamine.

  Moreover, as a hardening | curing agent used for a positive type dye containing curable composition, the following compounds (1)-(6) can also be mentioned.

  When using a hardening | curing agent for the said positive type dye containing curable composition, the content shall be 10-35 mass parts normally with respect to 100 mass parts of total amounts of each pigment | dye, a photosensitive agent, and alkali-soluble resin. preferable.

  The positive dye-containing curable composition is usually used after diluted with a solvent. The solvent is appropriately selected and used in accordance with the solubility of each dye used (dyes (I) to (IV)), the photosensitizer, the alkali-soluble resin and the curing agent, and particularly the solubility of the dyes (I) to (IV). For example, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, N, N′-dimethylformamide, cyclohexane, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, ethyl acetate, ethyl pyruvate, ethyl lactate and the like can be used. These solvents may be used alone or in combination of two or more. The amount of the solvent used is usually about 180 to 400 parts by mass with respect to 100 parts by mass of the total amount of each dye, photosensitizer, alkali-soluble resin and curing agent.

-Negative type photopolymerizable layer-
In the case where the photopolymerizable layer in the present invention is configured as a negative type, in addition to the above-described configuration, a photoacid generator, a curing agent, and an alkali-soluble resin can be included in addition to the dye. Hereinafter, a negative dye-containing curable composition containing a photoacid generator that can be used to form a photopolymerizable layer having such a configuration may be referred to as a “second negative dye-containing curable composition”. is there.
As the photoacid generator, the same photoacid generator as that used in ordinary negative dye-containing curable compositions can be used. For example, a compound represented by the following general formula (D) can be used. Can be mentioned.

［式中、Ｑ⁷は炭素数１〜３のアルキル基を示し、Ｑ⁸は炭素数１〜３のアルキル基で置換されたフェニル基または炭素数１〜３のアルコキシル基で置換されたフェニル基を示す。］

[Wherein Q ⁷ represents an alkyl group having 1 to 3 carbon atoms, and Q ⁸ represents a phenyl group substituted with an alkyl group having 1 to 3 carbon atoms or a phenyl group substituted with an alkoxyl group having 1 to 3 carbon atoms. Indicates. ]

The alkyl group having 1 to 3 carbon atoms represented as the Q ^7, for example, a methyl group, an ethyl group, a propyl group. As the phenyl group substituted with an alkyl group having 1 to 3 carbon atoms represented as Q ^8, for example, such as o- isopropylphenyl group. Examples of the phenyl group substituted with an alkoxyl group having 1 to 3 carbon atoms include a p-methoxyphenyl group, a p-ethoxyphenyl group, and a p-propoxyphenyl group.

Further, as the photoacid generator, the following compounds (7) to (13) can also be used.

  In addition, as the curing agent, the above-described heating curing agent that is cured by heating can be used in the same manner as used in a normal negative dye-containing curable composition.

  As the alkali-soluble resin, the same alkali-soluble resin as exemplified in the positive type dye-containing curable composition can be used as in the case of a normal negative type dye-containing curable composition. .

  In the second negative dye-containing curable composition, the content of the photoacid generator, the curing agent, and the alkali-soluble resin is 100, which is the total amount of each pigment, photoacid generator, curing agent, and alkali-soluble resin. It is preferable that the total content of each pigment is usually about 15 to 40 parts by mass, and the content of the photoacid generator is usually about 0.3 to 5 parts by mass with respect to parts by mass, and curing. It is preferable that the usage-amount of an agent is normally about 10-25 mass parts, and it is preferable that content of alkali-soluble resin is about 20-75 mass parts normally.

  The second negative photosensitive resin composition is also usually used after diluted with a solvent. The solvent is preferably selected as appropriate depending on the solubility of the pigments (I) to (IV), the solubility of the pigments (I) to (IV), and the solubility of the pigments (I) to (IV). . As the solvent, the same solvents as those exemplified above for the organic solvent and the positive dye-containing curable composition can be used. The usage-amount of a solvent is about 180-400 mass parts normally with respect to 100 mass parts of total amounts of each pigment | dye, a photo-acid generator, a hardening | curing agent, and alkali-soluble resin.

<PVA layer>
The photocurable image recording material of the present invention has a PVA layer containing polyvinyl alcohol on the photopolymerizable layer of the present invention.
The polyvinyl alcohol is preferably selected from those containing polyvinyl alcohol and derivatives thereof.
By applying the PVA layer as an upper layer of the photopolymerizable layer, the PVA layer functions as an oxygen blocking film, and can inhibit inhibition of radical polymerization by oxygen.

In order for the polyvinyl alcohol applicable to the present invention to have an oxygen-blocking function, those having a high degree of saponification are preferred. Specifically, the degree of saponification is preferably 70% or more, and more preferably 80% or more. Such polyvinyl alcohol is commercially available. For example, “Kuraray Poval Series” of Kuraray Co., Ltd. has various types of saponification, and is used alone or in combination of two or more depending on the purpose. be able to.
As a specific product name, as a completely saponified polyvinyl alcohol, Kuraray Poval series (PVA-103, PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA- 126H, PVA-135H, PVA-CSA, PVA-CST, PVA-HC), etc. In the case of intermediate saponified polyvinyl alcohol, Kuraray Poval series (PVA-617, PVA-624, PVA-613, PVA-706, PVA-610) Is mentioned.
Moreover, in partially saponified polyvinyl alcohol, Kuraraypoval (PVA-203, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-228, PVA-228, PVA-228, PVA-235 is used. , PVA-217E, PVA-217E, PVA-217EE, PVA-220E, PVA-224E, PVA-317, PVA-403, PVA-405, PVA-420, PVA-420H, PVA-424H, L-8, L -9, L-9-78, L-10). Further, as a low saponification product, Kuraray Poval PVA-505 is preferably used.

As the polyvinyl alcohol derivative, those modified for the purpose of increasing the surface activity and reactivity in addition to the purpose of blocking oxygen can be used. An example of the polyvinyl alcohol derivative is illustrated below. These may be used alone or in combination of two or more. Moreover, the said polyvinyl alcohol derivative can also be mixed and used for the above-mentioned polyvinyl alcohol.
Examples of the polyvinyl alcohol derivative include KL-504, KL-506, KL-318, KL-118, KM-618, KM-118, and C-, which are commercially available from Kuraray Co., Ltd. as Kuraray functional polymers. 506, C-318, C-118, CM-318, R-1130, R-2150, R-2130, M-205, M-115, MP-103, MP-102, MP-202, HL-12E, HL- 1203, HL-12E, HL-1203, SK-5102, LM-10HD, LM-15, LM-20, LM-25, etc. are mentioned.
In addition, the polyvinyl alcohol derivative may be commercially available in liquid form, and examples thereof include “CP” series manufactured by Fuji Film Arch Co., Ltd.
The PVA layer may be composed only of polyvinyl alcohol, or may contain other additives.

  The amount of polyvinyl alcohol added in the polyvinyl alcohol solution used for forming the PVA layer is not limited as long as it is an amount that dissolves in a solution such as water, but is preferably 0.01% by mass to 80% by mass, 0.1 mass%-50 mass% are still more preferable, and 1 mass%-25 mass% are especially preferable.

  The thickness of the PVA layer is preferably 0.01 μm to 5 μm, more preferably 0.1 μm to 2 μm, from the viewpoint of oxygen barrier properties.

<Support>

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

<Color filter and manufacturing method thereof>
Next, the photocurable image recording material and color filter of the present invention will be described in detail through the production method thereof.
In the method for producing a color filter of the present invention, the aforementioned aqueous solution containing PVA and a dye-containing curable composition can be used.
The photocurable image recording material of the present invention comprises a xanthene dye having an absorption maximum at least at a wavelength of 500 to 600 nm, a pyrazolone azo dye having an absorption maximum at a wavelength of 400 to 550 nm, and a radical polymerizable monomer. The dye-containing curable composition containing is coated by a coating method such as spin coating, cast coating, roll coating, etc., and then the solution containing the polyvinyl alcohol is coated, and the photopolymerizable layer and the PVA layer on the support. Are provided in this order.

In the method for producing a color filter of the present invention, the surface of the photocurable image recording material of the present invention on which the photopolymerizable layer is provided is exposed through a mask and developed to form a pattern. Thus, the color filter of the present invention can be produced.
That is, in the method for producing a color filter of the present invention, at least a xanthene dye having an absorption maximum at a wavelength of 500 to 600 nm, a pyrazolone azo dye having an absorption maximum at a wavelength of 400 to 550 nm, and a radical polymerizable monomer. The dye-containing curable composition is applied on a support by a coating method such as spin coating, casting coating or roll coating to form a photopolymerizable layer, and then a polyvinyl alcohol aqueous solution is coated to form a PVA layer. Thereafter, the layer is exposed through a predetermined mask pattern and developed with a developer, whereby a negative coloring pattern can be formed (image forming step). Moreover, the hardening process which hardens | cures the formed coloring pattern by heating and / or exposure as needed may be included.

In the production of the color filter, a color filter having a desired hue can be produced by repeating the image forming step (and curing step if necessary) by the desired number of hues. As light or radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.
The transmittance of the photopolymerizable layer (red filter layer) in the present invention after patterning is 1% or less at a wavelength of 535 nm, preferably 90% or more at a wavelength of 650 nm, and 5% or less at a wavelength of 450 nm. More preferably.

  Any developer can be used as long as it has a composition that dissolves the uncured portion of the dye-containing curable composition and does not dissolve the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As said organic solvent, the above-mentioned solvent used when preparing the dye-containing curable composition of this invention is mentioned.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene, the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution obtained by dissolution is preferable. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

Moreover, a color filter array can be produced by combining another color layer with the color filter of the present invention. For example, the color filter array can be produced by providing the color filter of the present invention with a green colored layer (green filter layer) and a blue colored layer (blue filter layer).
The green filter layer preferably contains the dye (VII) described above and has a transmittance of 10% or less at a wavelength of 650 nm.

Each colored layer combined with the color filter (red) of the present invention can be produced by a normal color resist method by newly providing a green photopolymerizable layer.
For example, a green photopolymerizable layer can be formed using a dye-containing curable composition containing a green dye, and the layer can be formed by patterning this layer to form a green filter layer. . Here, the dye-containing curable composition containing the green dye preferably contains the pigment (IV) and the pigment (V), and the pigment (IV) and the pigment (V) in the dye-containing curable composition. The content of each is the same as the content in the target green filter layer. In addition, when the target green filter layer contains another pigment, for example, the pigment (VI) or the pigment (VII), a dye-containing curable composition containing the pigment (VI) or the pigment (VII) May be used. In this case, the content of the pigment (VI) and the pigment (VII) in the dye-containing curable composition is the same as the content in the target green filter layer.
Further, the transmittance of the green filter layer after patterning is preferably 5% or less at a wavelength of 450 nm and 62% or more at a wavelength of 535 nm.

The blue colored layer (blue filter layer) can also be produced by a normal color resist method. For example, a blue photopolymerizable layer is formed using a dye-containing curable composition containing a blue dye. It can be formed by a manufacturing method having a step of patterning this layer to form a blue filter layer. Here, it is preferable that the dye-containing curable composition containing the blue dye contains the pigment (VIII). The content of the pigment (VIII) in the dye-containing curable composition is the same as the content in the target blue filter layer.
In addition, when the target blue filter layer contains another pigment, for example, pigment (IX) or pigment (X), a dye-containing curable composition containing pigment (IX) or pigment (X) is used. That's fine. In this case, the content of the dye (IX) and the dye (X) in the photosensitive resin composition is the same as the content in the target blue filter layer.
The transmittance of the blue filter layer after patterning is preferably 70% or more at a wavelength of 450 nm and 5% or less at a wavelength of 650 nm.
A color filter array comprising a red filter layer, a green filter layer, and a blue filter layer formed adjacent to each other on the same plane on a support can color a solid-state imaging device, a liquid crystal display device, etc. According to the solid-state imaging device in which the color filter array is disposed on the front side of the charge coupled device, a color image excellent in color reproducibility, particularly green color reproducibility can be obtained.

  The color filter of the present invention can be 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. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

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

<Production of photocurable image recording material>
(Preparation of photosensitive resin composition)
First, the following compositions were prepared.

<Red filter composition 1>
The following composition was mixed. Then, it filtered with the membrane filter with a hole diameter of 0.1 micrometer, and prepared the photosensitive resin thing (red filter composition 1).
〔composition〕
-Dye: Xanthene dye 1 below: 4 parts by mass-Dye: C.I. I. Solvent Orange 56 3 parts by mass / pigment: C.I. I. Solvent Yellow82 2 parts by mass, alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 70/30 molar ratio) 7.5 parts by mass Dipentaerythritol hexaacrylate 6.1 parts by weight photoinitiator ... 2 parts by mass (trade name: CGI-242, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Dye: C.I. I. Solvent Yellow162 2 parts by mass / solvent (ethyl lactate) 70 parts by mass

<Green filter composition 1>
The following composition was mixed. Then, it filtered with the membrane filter with a hole diameter of 0.1 micrometer, and prepared the photosensitive resin thing (green filter composition 1).
〔composition〕
-Dye: C.I. I. Solvent Blue 67 ... 2.5 parts by mass-Dye: C.I. I. Solvent Yellow162: 3.5 parts by mass Dye: C.I. I. Solvent Yellow82: 3.5 parts by mass, alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 70/30 molar ratio): 7.5 parts by mass, dipentaerythritol hexaacrylate: 6.1 parts by mass, photopolymerization Initiator: 2 parts by mass (trade name: CGI-242, manufactured by Ciba Specialty Chemicals Co., Ltd.)
・ Solvent (ethyl lactate): 70 parts by mass

<Blue filter composition 1>
The following composition was mixed. Then, it filtered with the membrane filter with a hole diameter of 0.1 micrometer, and prepared the photosensitive resin thing (blue filter composition 1).
〔composition〕
-Dye: C.I. I. Acid Blue 83 ... 20 parts by mass-Dye: C.I. I. Solvent Blue 67 ... 10 parts by mass Photopolymerization initiator ... 2 parts by mass (trade name: CGI-242, manufactured by Ciba Specialty Chemicals Co., Ltd.)
Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 70/30 molar ratio) 7.5 parts by mass Dipentaerythritol hexaacrylate 6.1 parts by weight Curing agent (hexamethoxymethylmelamine) 15 Part by mass / solvent (ethyl lactate): 300 parts by mass

<Red filter composition 2>
The following composition was mixed. Then, it filtered with the membrane filter with a hole diameter of 0.1 micrometer, and prepared the photosensitive resin thing (red filter composition 2).
〔composition〕
-Dye: Dye for comparison as follows: 4 parts by mass-Dye: C.I. I. Solvent Orange 56 3 parts by mass / pigment: C.I. I. Solvent Yellow82 2 parts by mass / Dye: C.I. I. Solvent Yellow 162 2 parts by mass, alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 70/30 molar ratio) 7.5 parts by mass Dipentaerythritol hexaacrylate 6.1 parts by weight photoinitiator ... 2 parts by mass (trade name: CGI-242, manufactured by Ciba Specialty Chemicals Co., Ltd.)
・ Solvent (ethyl lactate): 70 parts by mass

<Green filter composition 2>
The following composition was mixed. Then, it filtered with the membrane filter with a hole diameter of 0.1 micrometer, and prepared the photosensitive resin thing (green filter composition 2).
〔composition〕
-Dye: C.I. I. Solvent Blue 67 ... 2.5 parts by mass-Dye: C.I. I. Acid Yellow 40: 7 parts by mass Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 70/30 molar ratio) 7.5 parts by mass Dipentaerythritol hexaacrylate 6.1 parts by mass Agent: 2 parts by mass (trade name: CGI-242, manufactured by Ciba Specialty Chemicals Co., Ltd.)
・ Solvent (ethyl lactate): 70 parts by mass

(Production of silicon wafer with undercoat layer)
Next, a resist solution (trade name: CT-2000L, manufactured by FUJIFILM Arch Corporation) is applied to a 6-inch silicon wafer using a spin coater so as to have a dry film thickness of 2 μm, and heated at 220 ° C. for 1 hour. It dried and formed the cured film (undercoat layer).
[Example 1]
<Preparation of the red photocurable image recording material of the present invention>
(Formation of red photopolymerizable layer)
The obtained red filter composition 1 was applied onto the silicon wafer with an undercoat layer using a spin coater so as to have a film thickness of 1.5 μm, and pre-baked at 100 ° C. for 120 seconds to obtain a red photopolymerizable layer. Formed.

(Formation of PVA layer)
On the red photopolymerizable layer comprising the red filter composition 1, a polyvinyl alcohol solution having the following composition is applied with a spin coater so that the dry film thickness is 1.0 μm, thereby forming a polyvinyl alcohol layer. A photocurable image recording material was prepared.
〔composition〕
・ Polyvinyl alcohol: 15 parts by mass (trade name: Kuraray Poval 205, manufactured by Kuraray Co., Ltd.)
・ Water: 85 parts by mass

<Production of color filter>
Next, using an i-line stepper exposure apparatus, the red photopolymerizable layer was subjected to pattern exposure of 2 μm at a wavelength of 365 nm. After the exposure, development was performed at 23 ° C. for 60 seconds using a developer (trade name: CD-2000, manufactured by Fuji Film Arch Co., Ltd.). Subsequently, after rinsing with running water for 20 seconds, spray drying was performed to obtain a pattern image. Thereafter, the wafer was heated at 200 ° C. for 10 minutes to obtain a final image, and a color filter was produced.

[Example 2]
In Example 1, except that polyvinyl alcohol in the polyvinyl alcohol solution was changed to 15 parts by mass of Kuraray Poval 105 (manufactured by Kuraray Co., Ltd.), a photocurable image recording material and a color filter were prepared in the same manner as in Example 1. Produced.

[Example 3]
Example 1 and Example 1 except that polyvinyl alcohol in the polyvinyl alcohol solution was changed to 7 parts by mass of Kuraray Poval 103 (manufactured by Kuraray Co., Ltd.) and 8 parts by mass of Kuraray Poval 203 (manufactured by Kuraray Co., Ltd.). Similarly, a photocurable image recording material and a color filter were produced.

[Example 4]
In Example 1, a photocurable image recording material and a color filter were produced in the same manner as in Example 1 except that “CP” manufactured by Fuji Film Arch Co., Ltd. was used instead of the polyvinyl alcohol solution.

[Example 5]
In Example 1, a photocurable image recording material and a color were prepared in the same manner as in Example 1 except that the polyvinyl alcohol in the polyvinyl alcohol solution was replaced with “Kuraray Functional Polymer KM-118” manufactured by Kuraray Co., Ltd. A filter was produced.

[Comparative Example 1]
In Example 1, a photocurable image recording material and a color filter were produced in the same manner as in Example 1 except that the upper layer polyvinyl alcohol solution was not applied.

[Comparative Example 2]
A photocurable image recording material and a color filter were produced in the same manner as in Example 1 except that the red filter composition 1 was changed to the red filter composition 2 in Example 1.

<Evaluation>
(1) Pattern rectangularity About the rectangularity of the pattern before and behind heating at 200 degreeC for 10 minute (s), the cross-sectional observation of the pattern was performed in SEM, and it evaluated according to the following reference | standard. The results are shown in Table 1 below.
[Standard]
○: The corners were not rounded but rectangular.
Δ: Some roundness was observed at the corners.
X: The roundness of a corner was recognized notably.

(2) Sensitivity Regarding the sensitivity of each photocurable image recording material, the minimum exposure amount at which a 2 μm square pattern can be confirmed was measured, and the measured value was used as an index of sensitivity. The smaller the measured value, the higher the sensitivity. The results are shown in Table 1 below.

  As shown in Table 1 above, by providing a photopolymerizable layer using the dye in the present invention, and a PVA layer as an upper layer thereof, oxygen blocking is performed, and the rectangularity of the pattern is very high with high sensitivity. Furthermore, a preferable photo-curable image-recording material was obtained with very little change due to heating after development.

[Examples 6 to 10]
(Formation of green photopolymerizable layer)
On the silicon wafer of the color filter obtained in Examples 1 to 5, the green filter composition 1 obtained above was applied using a spin coater so that the dry film thickness was 1.5 μm, and 100 ° C. For 120 seconds to form a green photopolymerizable layer.

(Formation of PVA layer)
On the green photopolymerizable layer comprising the green filter composition 1, a polyvinyl alcohol solution having the following composition is applied with a spin coater so that the dry film thickness is 1.0 μm, thereby forming a polyvinyl alcohol layer. A photocurable image recording material was prepared.
〔composition〕
・ Polyvinyl alcohol: 15 parts by mass (trade name: Kuraray Poval 205, manufactured by Kuraray Co., Ltd.)
・ Water: 85 parts by mass

<Production of color filter>
Next, using an i-line stepper exposure apparatus, the green photopolymerizable layer was subjected to pattern exposure of 2 μm at a wavelength of 365 nm. After the exposure, development was performed at 23 ° C. for 60 seconds using a developer (trade name: CD-2000, manufactured by Fuji Film Arch Co., Ltd.). Subsequently, after rinsing with running water for 20 seconds, spray drying was performed to obtain a pattern image. Thereafter, the wafer was heated at 200 ° C. for 10 minutes to obtain a final image, and a color filter was produced.
The results of evaluating the sensitivity of the green photopolymerizable layer and the rectangularity of the green image in the same manner as in Example 1 are shown in Table 2 below.

[Comparative Example 3]
In Example 6, a photocurable image recording material and a color filter were produced in the same manner as in Example 6 except that the polyvinyl alcohol solution was not applied on the red photopolymerizable layer and the green photopolymerizable layer. The results of evaluating the sensitivity of the green photopolymerizable layer and the rectangularity of the green image in the same manner as in Example 1 are shown in Table 2 below.

[Comparative Example 4]
A photocurable image was obtained in the same manner as in Example 1 except that the red filter composition 1 was changed to the red filter composition 2 and the green filter composition 1 was changed to the green filter composition 2 in Example 6. Recording materials and color filters were produced. The results of evaluating the sensitivity of the green photopolymerizable layer and the rectangularity of the green image in the same manner as in Example 1 are shown in Table 2 below.

[Examples 11 to 15]
(Formation of blue photopolymerizable layer)
Spin the blue filter composition 1 obtained above on the color filter silicon wafer on which the red image and the green image obtained in Examples 6 to 10 were formed so that the dry film thickness was 1.5 μm. It was coated using a coater and pre-baked at 100 ° C. for 120 seconds to form a blue photopolymerizable layer.

(Formation of PVA layer)
On the green photopolymerizable layer comprising the blue filter composition 1, a polyvinyl alcohol solution having the following composition is applied with a spin coater so that the dry film thickness is 1.0 μm, thereby forming a polyvinyl alcohol layer. A photocurable image recording material was prepared.
〔composition〕
・ Polyvinyl alcohol: 15 parts by mass (trade name: Kuraray Poval 205, manufactured by Kuraray Co., Ltd.)
・ Water: 85 parts by mass

<Production of color filter>
Then, using an i-line stepper exposure apparatus, the blue photopolymerizable layer was subjected to pattern exposure of 2 μm at a wavelength of 365 nm. After the exposure, development was performed at 23 ° C. for 60 seconds using a developer (trade name: CD-2000, manufactured by Fuji Film Arch Co., Ltd.). Subsequently, after rinsing with running water for 20 seconds, spray drying was performed to obtain a pattern image. Thereafter, the wafer was heated at 200 ° C. for 10 minutes to obtain a final image, and a color filter was produced.
The results of evaluating the sensitivity of the blue photopolymerizable layer and the rectangularity of the blue image in the same manner as in Example 1 are shown in Table 3 below.

[Example 16]
A color filter array was produced using the photocurable image recording materials of red, green and blue obtained in Examples 1, 6 and 11, and a microlens was formed to produce a solid-state imaging device. Each image (color filter) was evaluated in the same manner as in Example 1. As a result, a color filter array having a very high rectangularity and excellent spectral characteristics was obtained as in Examples 1-15.

Claims (3)

  On the support, a photopolymerizable layer containing a xanthene dye having an absorption maximum at a wavelength of 500 to 600 nm, a pyrazolone azo dye having an absorption maximum at a wavelength of 400 to 550 nm, and a radical polymerizable monomer, and a layer containing polyvinyl alcohol, And a photocurable image-recording material having the above-mentioned in this order.   A color filter comprising the photocurable image recording material according to claim 1.   A color filter comprising: a step of exposing a surface of the photocurable image recording material according to claim 1 on which the photopolymerizable layer is provided through a mask, and developing to form a pattern. Production method.