JP2013068814A - Colored radiation-sensitive composition, color filter and method of producing the same, and solid-state image sensor - Google Patents

Abstract

Disclosed is a colored radiation-sensitive composition that can form a colored pattern with good linearity and that suppresses the generation of residues outside the colored pattern formation region.
The composition comprises (A) a colorant, (B) an acrylic resin having a partial structure represented by the following formula (I), (C) a polymerizable compound, and (D) an ultraviolet absorber. The colored radiation-sensitive composition whose content of a ultraviolet absorber is 0.1 mass%-10 mass% with respect to solid content of a colored radiation-sensitive composition.

[Selection figure] None

Description

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

  The color filter is an indispensable component for solid-state imaging devices and liquid crystal displays. In particular, color filters for solid-state imaging devices are required to improve color separation and color reproducibility.

  Such a color filter is formed to include a plurality of colored regions (colored cured films), and usually has at least red, green, and blue colored regions (hereinafter referred to as “colored patterns” and “colored”). It is also called a “pixel”. As a method for forming a colored pattern, first, in a first hue, a colored radiation-sensitive composition having a colorant of any one of red, green, and blue is applied on a substrate, exposed, developed, and as necessary. After the heat treatment is performed to form a colored pattern of the hue, the same coating, exposure, development, and heat treatment processes as necessary are repeated for the second hue and the third hue.

  As a colorant in a color filter, since it has a clear color tone and high coloring power, a pigment is widely used, and in particular, it is miniaturized and exhibits a suitable hue and color density, and has a color separation property. It is preferable to use good pigments.

In recent years, in solid-state imaging devices, it has been required to form fine colored patterns (for example, colored patterns with a side of 2.0 μm or less on a solid-state imaging device) with high reproducibility for the purpose of improving resolution. It is also required to reduce the film thickness of the pattern (for example, a film thickness of 1 μm or less for a solid-state imaging device).
However, if the size of the colored pattern is made fine, the linearity around the square colored pixels tends to be poor, and a residue that appears to be undeveloped tends to be generated on the substrate or other color pattern. For this reason, when a color filter is used for a solid-state image sensor, it is required to overcome the disadvantage that the color separation property is deteriorated and a solid-state image sensor with high resolution cannot be obtained.

  Various proposals have been made for techniques for improving the linearity of the coloring pattern and reducing the residue, but even with these techniques, the reduction of the residue generated on the pattern of other colors is still insufficient. A further technical improvement has been awaited.

  In addition, it is known that a polymer compound having a benzimidazole ring is used as a pigment dispersant to improve the dispersibility of the pigment (see, for example, Patent Document 1). There has been a demand for further improvement of the technique of forming the colored pattern, not the technique of paying attention to the linearity of the colored pattern or the reduction of the residue.

JP 2010-53307 A

An object of the present invention is to provide a colored radiation-sensitive composition that can form a colored pattern with good linearity and that suppresses the generation of residues outside the colored pattern formation region.
Another object of the present invention is to provide a color filter having a color pattern with good linearity and reduced residue outside the color pattern formation region, a method for manufacturing the same, and the color filter. A solid-state imaging device is provided.

The present inventors conducted intensive research in view of the above circumstances, and found that the above-described problems can be solved by the following means, and completed the present invention.
Means for solving the above problems are as follows.

<1> (A) a colorant, (B) an acrylic resin having a partial structure represented by the following formula (I), (C) a polymerizable compound, and (D) an ultraviolet absorber, The colored radiation-sensitive composition whose content of an absorber is 0.1 mass%-10 mass% with respect to solid content of a colored radiation-sensitive composition.

  In formula (I), R represents a hydrogen atom or a monovalent substituent. * Represents the site of binding to the main chain structure.

<2> The colored radiation-sensitive composition according to <1>, wherein the acrylic resin having the partial structure represented by formula (I) is an acrylic resin further containing a carboxyl group.
<3> The content of the partial structure represented by the formula (I) contained in the acrylic resin having the partial structure represented by the formula (I) (B) is 1% by mass to the total amount of the acrylic resin. The colored radiation-sensitive composition according to <1> or <2>, which is 30% by mass.

<4> The colored radiation-sensitive composition according to any one of <1> to <3>, wherein the colorant (A) is a red pigment.
<5> The colored radiation-sensitive composition according to any one of <1> to <4>, wherein the (D) ultraviolet absorber is a compound represented by the following general formula (II).

In the general formula (II), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² And do not represent hydrogen atoms at the same time. R ³ and R ⁴ each independently represents a monovalent group.

<6> The polymerizable compound according to any one of <1> to <5>, wherein the polymerizable compound (C) is a polymerizable compound containing an ethyleneoxy group and five or more (meth) acryloyl groups in a molecule. Colored radiation-sensitive composition.
<7> The colored radiation-sensitive composition according to any one of <1> to <6>, further comprising (E) a photopolymerization initiator.
<8> The colored radiation-sensitive composition according to <7>, wherein the (E) photopolymerization initiator is an oxime compound.

<9> A color filter comprising a colored film using the colored radiation-sensitive composition according to any one of <1> to <8>.
<10> A step of forming a colored radiation-sensitive composition layer by applying the colored radiation-sensitive composition according to any one of <1> to <8> on a substrate, and the colored radiation-sensitive composition. A method for producing a color filter, comprising: exposing a composition layer in a pattern; and developing the colored radiation-sensitive composition layer after exposure to form a colored pattern.
<11> A solid-state imaging device comprising the color filter according to <9>.

  The colored radiation-sensitive composition of the present invention comprises a colorant, an acrylic resin having a partial structure represented by formula (I), a polymerizable compound, and an ultraviolet absorber. The mechanism for improving the linearity of the colored pattern and reducing the residue in the present invention is not clear, but is presumed as follows. That is, in the exposure process, the ultraviolet light contained prevents the exposure light from entering the non-exposed part by reflection or the like in the colored radiation-sensitive composition layer, and the latent image is formed only in the exposed part. It is thought that. On the other hand, in the development step, the structure of the formula (I) interacts with the colorant, and particularly when a pigment is used as the colorant, the structural part of the formula (I) is adsorbed to the pigment, It is considered that the acrylic resin is easily dissolved in the developer. By these actions, it is considered that the linearity of the obtained colored pattern is improved and the residue outside the colored pattern forming region (on the substrate and the colored patterns of other colors) is reduced. In particular, when the compound represented by the general formula (II) is used as an ultraviolet absorber, it suppresses subsequent development performance fluctuations particularly when low-illuminance exposure is performed. Dependence on exposure illuminance related to pattern formability such as the above can be suppressed, lowering of sensitivity due to the addition of an ultraviolet absorber is suppressed, and the linearity of the colored pattern, which is an effect of the present invention, and reduction of residues are reduced. It seems that we were able to plan.

ADVANTAGE OF THE INVENTION According to this invention, the colored radiation sensitive composition which can form a coloring pattern with favorable linearity, and generation | occurrence | production of the residue outside a coloring pattern formation area was suppressed can be provided.
Further, according to the present invention, a color filter having a colored pattern with good linearity and having reduced residue outside the colored pattern forming region, a method for manufacturing the same, and a solid-state imaging device including the color filter An element can be provided.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below is made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

In the colored radiation-sensitive composition of the present invention, the total solid content means the total mass of components excluding the organic solvent from the total composition of the colored radiation-sensitive composition.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

In the present specification, the “alkyl group” refers to a “straight chain, branched, and cyclic” alkyl group, and may be substituted or unsubstituted.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acrylic”. ) "Acryloyl" represents both and / or acryloyl and methacryloyl.

  In the present specification, “monomer” and “monomer” are synonymous. The monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.

  In addition, in the description of groups (atomic groups) in the present specification, the description that does not indicate substitution and non-substitution includes those having no substituent and those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In the present invention, “radiation” means a substance containing visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like.

The colored region in the color filter of the present invention includes a colored pixel (colored pattern) region and a light shielding film forming region in the color filter.
Further, the substrate on which the colored radiation-sensitive composition of the present invention is provided will be described in detail later, but an undercoat layer may be provided on a photoelectric conversion element substrate, a silicon substrate, etc. Even if the pattern is formed using the colored radiation-sensitive composition of the present invention, it is formed using a colored radiation-sensitive composition that is different from the colored radiation-sensitive composition of the present invention. It may be.

[Colored radiation-sensitive composition]
The colored radiation-sensitive composition of the present invention comprises at least (A) a colorant and (B) an acrylic resin containing a partial structure represented by the following formula (I) (hereinafter referred to as “specific resin” as appropriate). , (C) a polymerizable compound, and (D) an ultraviolet absorber, wherein the content of the (D) ultraviolet absorber is 0.1% by mass to 10% by mass with respect to the solid content of the colored radiation-sensitive composition. %.

  In formula (I), R represents a hydrogen atom or a monovalent substituent. * Represents the site of binding to the main chain structure.

Examples of the monovalent substituent represented by R include a linear alkyl group, a branched alkyl group, a hydroxyl group, a nitro group, and a sulfo group.
Of these, a linear alkyl group and a branched alkyl group, and a methyl group and an ethyl group are preferable.

  Hereinafter, each component contained in the colored radiation-sensitive composition of the present invention will be described in detail.

<(A) Colorant>
The colored radiation-sensitive composition of the present invention contains a colorant. The colorant may be a pigment or a dye. Further, as the colorant, two or more kinds of pigments, two or more kinds of dyes, or one or more kinds of pigments and one or more kinds of dyes may be used in combination.
The colored radiation-sensitive composition of the present invention is preferably a red, green, and blue colored radiation-sensitive composition, and can also be applied to a complementary color cyan, magenta, or yellow colored radiation-sensitive composition. It is. Preferably, red, green, and blue colored radiation-sensitive compositions, and when applied to a red colored radiation-sensitive composition, a great effect is obtained, and in particular, a colored radiation-sensitive composition using a red pigment. By applying to objects, even greater effects can be obtained.
Below, the colorant which a red, green, and blue coloring radiation sensitive composition contains is demonstrated.

[Red colored radiation-sensitive composition]
The red colored radiation sensitive composition includes red and orange pigments or dyes. Further, a yellow pigment or dye may be included. Two or more red colorants, two or more red colorants and a yellow colorant, a red colorant and two or more yellow colorants, or two or more red colors may be used. An agent and two or more yellow colorants may be used.

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279
Examples of orange pigments include C.I. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. It is.

  Examples of red dyes include C.I. I. 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, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274, etc.

  Among these red and orange colorants, C.I. from the viewpoint of suppressing the linearity of the coloring pattern and the generation of residues. I. Pigment Red 166, 177, 224, 242, and 254 are preferable. I. Pigment Red 254 is preferred.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 17 , It is a 176,177,179,180,181,182,185,187,188,193,194,199,213,214, and the like.

  Examples of yellow dyes include C.I. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; I. Hood Yellow 3 etc. can be mentioned.

  Among these yellow colorants, C.I. from the viewpoint of suppressing the linearity of the coloring pattern and the generation of residues. I. Pigment Yellow 139 is preferable.

The content ratio of the red colorant and the yellow colorant in the red colored radiation-sensitive composition may be, based on mass, red colorant: yellow colorant = 80: 20 to 60:40. 70:30 is particularly preferable.
The content of the total colorant in the red colored radiation-sensitive composition is preferably 10% to 40% on a mass basis with respect to the total solid content of the red colored radiation-sensitive composition. More preferably, it is 20% to 30%.

[Green colored radiation-sensitive composition]
The green colored radiation-sensitive composition contains a green pigment or dye. Further, a yellow pigment or dye may be included. Two or more green colorants and a yellow colorant may be used, or a green colorant and two or more yellow colorants may be used, or two or more green colorants and two or more yellow colorants are used. May be.

Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58, etc.
Examples of the green dye include C.I. I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, etc.

  Among these green colorants, C.I. I. Pigment Green 7, 36 and 58 are preferable. I. Pigment Green 36 and 58 are preferable.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 17 , It is a 176,177,179,180,181,182,185,187,188,193,194,199,213,214, and the like.

  Examples of yellow dyes include C.I. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; I. Hood Yellow 3 etc. can be mentioned.

  Among these yellow colorants, C.I. I. Pigment Yellow 139, 150, and 185 are preferable.

The content ratio of the green colorant and the yellow colorant in the green colored radiation-sensitive composition is, on a mass basis, green colorant: yellow colorant = 50: 50 to 70:30. It is preferably 60:40.
Further, the content of the total colorant in the green colored radiation-sensitive composition is preferably 10% to 40% on a mass basis with respect to the total solid content of the green colored radiation-sensitive composition. More preferably, it is 20% to 30%.

[Blue colored radiation-sensitive composition]
The blue colored radiation-sensitive composition contains a blue pigment or dye. Further, a purple pigment or dye may be included. Only a blue colorant may be sufficient, 2 or more types of blue colorants and purple colorants may be sufficient, a blue colorant and 2 or more types of purple colorants may be sufficient, or 2 or more types of blue colorants and 2 types You may use the above purple colorant.

Examples of the blue pigment include C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, and the like.
Examples of the blue dye include C.I. I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40-45, 62, 70, 74, 80, 83, 86, 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1 and the like.

  Among these blue colorants, C.I. I. Pigment Blue 15: 3 and 15: 6 are preferable. I. Pigment Blue 15: 6 is preferable.

  Examples of purple pigments include C.I. I. Pigment violet 1, 19, 23, 27, 32, 37, 42 and the like.

Examples of purple dyes include C.I. I. Acid Violet 6B, 7, 9, 17, 19, C.I. I. And acid chrome violet K3.
As the purple dye, a dipyrromethene dye represented by the following general formula (M) is also preferable.

[Dipyrromethene dye represented by general formula (M) = specific dye]
The blue pixel in the present invention preferably contains a dipyrromethene dye represented by the following general formula (M) (hereinafter referred to as “specific dye” as appropriate).
The specific dye may be a dipyrromethene dye represented by the following general formula (M), and is derived from a dipyrromethene metal complex compound obtained from the general formula (M) and a metal or a metal compound, or a tautomer thereof. Includes structure.

[In General Formula (M), R ^{4 to} R ¹⁰ each independently represents a hydrogen atom or a monovalent substituent. However, R ⁴ and R ⁹ are not bonded to each other to form a ring. ]

Specific examples of the dipyrromethene metal complex compound obtained from the dipyrromethene compound represented by the general formula (M) and a metal or a metal compound or a tautomer thereof include the following general formula (5) or the following general formula ( The dipyrromethene metal complex compound represented by 6) is mentioned.
However, the present invention is not limited to these.

(Dipyrromethene metal complex compound represented by the general formula (5))

In the general formula (5), R ^{4 to} R ⁹ each independently represents a hydrogen atom or a substituent, and R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound. X ¹ represents a group capable of binding to Ma, X ² represents a group that neutralizes the charge of Ma, and X ¹ and X ² are bonded to each other to form a 5-membered, 6-membered, or 7-membered member together with Ma. The ring may be formed. However, R ⁴ and R ⁹ are not bonded to each other to form a ring. In addition, the dipyrromethene metal complex compound represented by the general formula (5) includes a tautomer.

There is no particular limitation on the site where one or two hydrogen atoms are removed from the dipyrromethene metal complex compound represented by the general formula (5) in order to form a dye residue, but in terms of synthesis compatibility, R ⁴ preferably any one or two sites to R ^9, R ^4, R 6, either one or two sites of ^{R 7} and ^{R 9} are more preferred, any one of ^{R 4} and ^{R 9} or Two sites are more preferred.

The specific dye in the present invention preferably has an alkali-soluble group.
As a method for introducing an alkali-soluble group into a specific dye, when a pigment monomer or a structural unit having an alkali-soluble group is used, R ^{4 to} R ¹⁰ of the dipyrromethene metal complex compound represented by the general formula (5), X Any one or two or more substituents of ¹ and X ² can have an alkali-soluble group. Among these substituents, any ^one of R ^{4 to} R ⁹ and X ¹ is preferable, any of R ⁴ , R ⁶ , R ⁷ and R ⁹ is more preferable, and any of R ⁴ and R ⁹ is still more preferable.

  The dipyrromethene metal complex compound represented by the general formula (5) may have a functional group other than the alkali-soluble group as long as the effects of the present invention are not impaired.

As said R < ⁴ > -R < ⁹ >, a halogen atom (for example, fluorine, chlorine, bromine), an alkyl group (preferably C1-C48, More preferably, C1-C24 linear, branched chain, Or a cyclic alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as vinyl, allyl, 3-buten-1-yl), an aryl group (preferably carbon An aryl group having 6 to 48, more preferably 6 to 24 carbon atoms, such as phenyl and naphthyl A heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2 -Benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), a silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, such as trimethylsilyl, triethylsilyl, Tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxy group, cyano group, nitro group, alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, , Methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecylo A cycloalkyloxy group such as cyclopentyloxy or cyclohexyloxy) or an aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms such as phenoxy or 1-naphthoxy ), A heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), silyloxy A group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably having 2 to 2 carbon atoms). 48, more preferably an acyloxy group having 2 to 24 carbon atoms, For example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as ethoxycarbonyloxy, t- Butoxycarbonyloxy, cycloalkyloxycarbonyloxy (for example, cyclohexyloxycarbonyloxy)), aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, , Phenoxycarbonyloxy), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy, N- Tilcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy), a sulfamoyloxy group (preferably having 1 to 32 carbon atoms, more preferably having 1 to 24 carbon atoms). , For example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, For example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy),

An arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as phenylsulfonyloxy), an acyl group (preferably having 1 to 48 carbon atoms, more preferably carbon An acyl group having 1 to 24, for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably an alkoxy having 2 to 24 carbon atoms) Examples of carbonyl groups include methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl), and aryloxycarbonyl groups (preferably having 7 to 32 carbon atoms). , Yo Preferably, it is an aryloxycarbonyl group having 7 to 24 carbon atoms, such as phenoxycarbonyl, and a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably a carbamoyl group having 1 to 24 carbon atoms, such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methylN-phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), amino A group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino), anilino Group (preferably having 6 to 32 carbon atoms) More preferably, it is an anilino group having 6 to 24 carbon atoms, such as anilino or N-methylanilino), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic amino group having 1 to 18 carbon atoms, For example, 4-pyridylamino), carbonamido group (preferably a carbonamido group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, acetamido, benzamido, tetradecanamido, pivaloylamide, cyclohexaneamido), ureido group (Preferably a ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido, N, N-dimethylureido, N-phenylureido), an imide group (preferably having 36 or less carbon atoms, more Preferably it is an imide group having 24 or less carbon atoms, such as N-succinimide and N-phthalate. Imide), alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonyl Amino, cyclohexyloxycarbonylamino), aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonylamino), sulfonamide group (preferably Is a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexane. Sulfonamides), sulfamoylamino groups (preferably sulfamoylamino groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino, N-ethyl). -N-dodecylsulfamoylamino), an azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenylazo, 3-pyrazolylazo),

An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, for example, methylthio, ethylthio, octylthio, cyclohexylthio), an arylthio group (preferably having 6 to 48 carbon atoms, more preferably An arylthio group having 6 to 24 carbon atoms, such as phenylthio, and a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, such as 2-benzothiazoli Ruthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably an alkylsulfinyl group having 1 to 24 carbon atoms, for example, dodecanesulfinyl group), an arylsulfinyl group ( Preferably it has 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms. An arylsulfonyl group (for example, phenylsulfinyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, Isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfonyl, 1-naphthylsulfonyl), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as sulfamoyl, N, N-dipropylsulfa , N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo group, phosphonyl group (preferably having 1 to 32 carbon atoms, more preferably carbon A phosphonyl group having 1 to 24 carbon atoms, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), phosphinoylamino group (preferably having 1 to 32 carbon atoms, more preferably phosphino having 1 to 24 carbon atoms) Ilylamino group includes, for example, diethoxyphosphinoylamino, dioctyloxyphosphinoylamino).

Among the above, R ⁴ and R ⁹ are preferably an alkylamino group, an arylamino group, a carbonamido group, a ureido group, an imide group, an alkoxycarbonylamino group, and a sulfonamido group, and a carbonamido group, a ureido group, an alkoxy group. A carbonylamino group and a sulfonamide group are more preferable, a carbonamide group, a ureido group, an alkoxycarbonylamino group, and a sulfonamide group are further preferable, and a carbonamide group and a ureido group are particularly preferable.
Among the above, R ⁵ and R ⁸ are preferably an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group, and an alkoxycarbonyl group, aryl Oxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group, carbamoylsulfonyl group are more preferable, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, nitrile group, imide group, carbamoylsulfonyl group are more preferable, alkoxy A carbonyl group, an aryloxycarbonyl group, and a carbamoyl group are particularly preferable.
Among the above, R ⁶ and R ⁷ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and more preferably a substituted or unsubstituted alkyl group. , A substituted or unsubstituted aryl group.

When R ⁶ and R ⁷ represent an alkyl group, the alkyl group is preferably a linear, branched, or cyclic substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, more specifically. For example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, i-butyl group, t-butyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and benzyl More preferably a branched chain having 1 to 12 carbon atoms or a cyclic substituted or unsubstituted alkyl group, and more specifically, for example, an isopropyl group, a cyclopropyl group, an i-butyl group, a t-butyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, and more preferably a secondary or tertiary substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. Ri, more specifically, for example, isopropyl, cyclopropyl, i- butyl, t- butyl group, a cyclobutyl group, a cyclohexyl group.

When R ⁶ and R ⁷ represent an aryl group, the aryl group preferably includes a substituted or unsubstituted phenyl group and a substituted or unsubstituted naphthyl group, and more preferably a substituted or unsubstituted phenyl group. It is a group.
When R ⁶ and R ⁷ represent a heterocyclic group, the heterocyclic group is preferably a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4-pyridyl group, a substituted or unsubstituted 3 -Pyridyl group, substituted or unsubstituted 2-pyridyl group, substituted or unsubstituted 2-furyl group, substituted or unsubstituted 2-pyrimidinyl group, substituted or unsubstituted 2-benzothiazolyl group, substituted or unsubstituted 1 -Imidazolyl group, substituted or unsubstituted 1-pyrazolyl group, substituted or unsubstituted benzotriazol-1-yl group, more preferably substituted or unsubstituted 2-thienyl group, substituted or unsubstituted 4- Examples include a pyridyl group, a substituted or unsubstituted 2-furyl group, a substituted or unsubstituted 2-pyrimidinyl group, and a substituted or unsubstituted 1-pyridyl group.

In the general formula (5), Ma represents a metal atom or a metal compound. The metal atom or metal compound may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or Divalent metal chlorides are included.
For example, Zn, Mg, Si, Sn , Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe , etc., and _{AlCl, InCl, FeCl, TiCl 2} , SnCl 2, SiCl 2, GeCl 2 , etc. Metal chlorides, metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are included.

  Among these, from the viewpoints of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, and VO are preferred, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, and VO are more preferred, Zn, Cu, Co, and VO are particularly preferred, and Zn is most preferred.

In the general formula (5), R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, preferably a hydrogen atom.

In the general formula (5), X ¹ may be any group as long as it is a group capable of binding to Ma. Specifically, water, alcohols (for example, methanol, ethanol, propanol), etc. The compounds described in “Metal Chelate” ([1] Takeichi Sakaguchi / Keihei Ueno (1995 Nanedo), [2] (1996), [3] (1997), etc.) can be mentioned. Among these, from the viewpoint of production, water, carboxylic acid compounds and alcohols are preferable, and water and carboxylic acid compounds are more preferable.

In the general formula (5), examples of the “group that neutralizes the charge of Ma” represented by X ² include a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group, and a sulfonic acid group. From the viewpoint of production, a halogen atom, a hydroxyl group, a carboxylic acid group, and a sulfonic acid group are preferable, and a hydroxyl group and a carboxylic acid group are more preferable.

In the general formula (5), X ¹ and X ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with Ma. The 5-membered, 6-membered and 7-membered rings formed may be saturated or unsaturated. The 5-membered, 6-membered, and 7-membered rings may be composed of only carbon atoms, and form a heterocycle having at least one atom selected from a nitrogen atom, an oxygen atom, and / or a sulfur atom. You may do it.

As a preferred embodiment of the compound represented by the general formula (5), R ^{4 to} R ⁹ are each independently a preferred embodiment described in the description of R ^{4 to} R ⁹ , and R ¹⁰ is a description of R ¹⁰ . In the preferred embodiment described, Ma is Zn, Cu, Co, or VO, X ¹ is water or a carboxylic acid compound, X ² is a hydroxyl group or a carboxylic acid group, and X ¹ and X ² May be bonded to each other to form a 5-membered or 6-membered ring.

(Dipyrromethene metal complex compound represented by the general formula (6))

In the general formula (6), R ¹¹ and R ¹⁶ are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. Represents a group. R ^{12 to} R ¹⁵ each independently represents a hydrogen atom or a substituent. R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound. X ² and X ³ are NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, an oxygen atom, or Represents a sulfur atom. Y ¹ and Y ² represent NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, or a carbon atom. Represent. R ¹¹ and Y ¹ may be bonded to each other to form a 5-, 6-, or 7-membered ring, and R ¹⁶ and Y ² are bonded to each other to form a 5-, 6-, or 7-membered ring. The ring may be formed. X ¹ represents a group capable of binding to Ma, and a represents 0, 1, or 2. In addition, the dipyrromethene metal complex compound represented by the general formula (6) includes a tautomer.

Although there is no particular limitation as a site where one or two hydrogen atoms are removed from the dipyrromethene metal complex compound represented by the general formula (6) in order to form a dye residue, R ^{11 to} R ¹⁷ , X ¹ , It is any one or two sites of Y ^{1 to} Y ² .
Among these, from the point of synthetic compatibility, any one or two sites of R ^{11 to} R ¹⁶ and X ¹ are preferable, and more preferably any one of R ¹¹ , R ¹³ , R ¹⁴ and R ^16. One or two sites, and more preferably one or two sites out of R ¹¹ and R ¹⁶ .

As a method for introducing an alkali-soluble group into the specific dye in the present invention, when a dye monomer or a structural unit having an alkali-soluble group is used, R ^{11 to} R of the dipyrromethene metal complex compound represented by the general formula (6). ¹⁷ , any one or two or more substituents of X ¹ , Y ^{1 to} Y ² may have an alkali-soluble group. Among these ^{substituents,} one of R 11 ^{～～R 16} and ^{X 1} are ^preferred, more preferably one of R ^11, R ^{13, R 14} and ^{R 16,} any one of ^{R 11} and ^{R 16} are more preferably .

  The dipyrromethene metal complex compound represented by the general formula (6) may have a functional group other than the alkali-soluble group as long as the effects of the present invention are not impaired.

Said R < ¹² > -R < ¹⁵ > is synonymous with R < ⁵ > -R < ⁸ > in the said General formula (5), and its preferable aspect is also the same. R ¹⁷ has the same meaning as R ¹⁰ in the general formula (5), and the preferred embodiment is also the same. Said Ma is synonymous with Ma in the said General formula (5), and its preferable range is also the same.

More specifically, in the general formula (6), among R ^{12 to} R ¹⁵ , the R ¹² and R ¹⁵ include an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, Nitrile group, imide group or carbamoylsulfonyl group is preferable, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group and carbamoylsulfonyl group are more preferable, alkoxycarbonyl group, aryloxycarbonyl Group, carbamoyl group, nitrile group, imide group and carbamoylsulfonyl group are more preferred, and alkoxycarbonyl group, aryloxycarbonyl group and carbamoyl group are particularly preferred.
R ¹³ and R ¹⁴ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, more preferably a substituted or unsubstituted alkyl group, substituted or unsubstituted. A substituted aryl group. Here, specific examples of more preferable alkyl groups, aryl groups, and heterocyclic groups can be the same as specific examples listed in R ⁶ and R ⁷ of the general formula (5).

In the general formula (6), R ¹¹ and R ¹⁶ are alkyl groups (preferably a linear, branched, or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl group (preferably having 2 to 24 carbon atoms, more preferably An alkenyl group having 2 to 12 carbon atoms, for example, vinyl, allyl, 3-buten-1-yl), an aryl group (preferably an aryl group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms, , Phenyl, naphthyl), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, For example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 2-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), an alkoxy group (preferably having 1 carbon atom) To 36, more preferably an alkoxy group having 1 to 18 carbon atoms, such as methoxy, ethoxy, propyloxy, butoxy, hexyloxy, 2-ethylhexyloxy, dodecyloxy, cyclohexyloxy), an aryloxy group (preferably having a carbon number) An aryloxy group having 6 to 24, more preferably 1 to 18 carbon atoms, such as phenoxy or naphthyloxy, an alkylamino group (preferably having 1 to 36 carbon atoms, more preferably an alkylamino group having 1 to 18 carbon atoms) For example, methylamino, ethylamino, propylamino, Tylamino, hexylamino, 2-ethylhexylamino, isopropylamino, t-butylamino, t-octylamino, cyclohexylamino, N, N-diethylamino, N, N-dipropylamino, N, N-dibutylamino, N-methyl -N-ethylamino), an arylamino group (preferably an arylamino group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms, such as phenylamino, naphthylamino, N, N-diphenylamino, N- Ethyl-N-phenylamino) or a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms such as 2-aminopyrrole, 3-aminopyrazole, 2 -Aminopyridine, 3-aminopyridine).

Among the above, R ¹¹ and R ¹⁶ are preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylamino group, an arylamino group, and a heterocyclic amino group, and an alkyl group, an alkenyl group, an aryl group, Heterocyclic groups are more preferred, alkyl groups, alkenyl groups, and aryl groups are more preferred, and alkyl groups are particularly preferred.

In the general formula (6), an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group represented by R ¹¹ and R ¹⁶ When it is a substitutable group, it may be substituted with the substituent explained in the substituent of R ^{1 in} the general formula (1) described later, and when it is substituted with two or more substituents These substituents may be the same or different.

In the general formula (6), X ² and X ³ represent NR, a nitrogen atom, an oxygen atom, or a sulfur atom. Here, R is a hydrogen atom, an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as methyl, ethyl, propyl, Isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms) An alkenyl group, for example, vinyl, allyl, 3-buten-1-yl), an aryl group (preferably an aryl group having 6 to 36 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms, for example, phenyl, naphthyl), A heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as 2-thienyl; 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), acyl group (preferably having 1 to 24 carbon atoms, more preferably An acyl group having 2 to 18 carbon atoms, for example, acetyl, pivaloyl, 2-ethylhexyl, benzoyl, cyclohexanoyl), an alkylsulfonyl group (preferably having 1 to 24 carbon atoms, more preferably an alkylsulfonyl having 1 to 18 carbon atoms) A group such as methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclohexylsulfonyl), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, such as phenylsulfonyl, naphthyl) Sulfonyl).

The alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkylsulfonyl group, and arylsulfonyl group of R are substituted with the substituent explained in the substituent of R ^{1 in} the general formula (1) described later. In the case where it is substituted with a plurality of substituents, these substituents may be the same or different.

In General Formula (6), Y ¹ and Y ² represent NR, a nitrogen atom, or a carbon atom, R has the same meaning as R in X ² and X ³ , and the preferred embodiment is also the same.

In the general formula (6), R ¹¹ and Y ¹ are bonded to each other to form a 5-membered ring with a carbon atom (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole, furan, thiophene, indole, benzofuran, Benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline), or 7-membered ring (eg, cyclo Heptane, hexamethyleneimine).

In the general formula (6), R ¹⁶ and Y ² are bonded to each other to form a 5-membered ring with a carbon atom (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole, furan, thiophene, indole, benzofuran, Benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline), or 7-membered ring (eg, cyclo Heptane, hexamethyleneimine).

In the general formula (6), when the 5-membered, 6-membered, and 7-membered rings formed by combining R ¹¹ and Y ¹ and R ¹⁶ and Y ² are substitutable rings, It may be substituted with the substituent described in the substituent of R ^{1 in} the general formula (1) described later, and when it is substituted with two or more substituents, the substituents are the same. May be different.

In the general formula (6), X ¹ represents a group capable of binding to Ma, and specific examples thereof include the same group as X ¹ in the general formula (5), and preferred embodiments are also the same. a represents 0, 1, or 2.

As a preferable aspect of the compound represented by the general formula (6), R ^{12 to} R ¹⁵ are each preferably a preferable aspect described in the description of R ^{5 to} R ^{8 in} the general formula (5). R ¹⁷ is a preferred embodiment described in the description of R ^{10 in} the general formula (5), Ma is Zn, Cu, Co, or VO, X ² is NR (R is a hydrogen atom, an alkyl group), A nitrogen atom or an oxygen atom, X ³ is NR (R is a hydrogen atom, an alkyl group), or an oxygen atom; Y ¹ is NR (R is a hydrogen atom, an alkyl group), a nitrogen atom, or a carbon atom; Y ² represents a nitrogen atom or a carbon atom, R ¹¹ and R ¹⁶ each independently represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, and X ¹ represents an oxygen atom. A is 0 or 1 A. R ¹¹ and Y ¹ may be bonded to each other to form a 5- or 6-membered ring, or R ¹⁶ and Y ² may be bonded to each other to form a 5- or 6-membered ring.

As a more preferable embodiment of the compound represented by the general formula (6), R ^{12 to} R ¹⁵ are each preferably independently described in the description of R ^{5 to} R ⁸ in the compound represented by the general formula (5). R ¹⁷ is a preferred embodiment described in the description of R ^{10 in} the general formula (5), Ma is Zn, X ² and X ³ are oxygen atoms, and Y ¹ is NH. Y ² is a nitrogen atom, R ¹¹ and R ¹⁶ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, and X ¹ is bonded through an oxygen atom. And a is 0 or 1. R ¹¹ and Y ¹ may be bonded to each other to form a 5- or 6-membered ring, or R ¹⁶ and Y ² may be bonded to each other to form a 5- or 6-membered ring.

The molar extinction coefficient of the dipyrromethene metal complex compound represented by the general formulas (5) and (6) is preferably as high as possible from the viewpoint of film thickness. The maximum absorption wavelength λmax is preferably 520 nm to 580 nm, more preferably 530 nm to 570 nm, from the viewpoint of improving color purity. The maximum absorption wavelength and molar extinction coefficient are measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation).
The melting point of the dipyrromethene metal complex compound represented by the general formula (5) and the general formula (6) is preferably not too high from the viewpoint of solubility.

  The dipyrromethene metal complex compounds represented by the general formula (5) and the general formula (6) are disclosed in U.S. Pat. Nos. 4,774,339, 5,433,896, and JP-A-2001-240761. 2002-155052 gazette, Japanese Patent No. 3614586 gazette, Aust. J. et al. Chem, 1965, 11, 1835-1845, J. Am. H. Boger et al, Heteroatom Chemistry, Vol. 1, No. 1 5,389 (1990) and the like. Specifically, the method described in paragraphs 0131 to 0157 of JP-A-2008-292970 can be applied.

The specific dye in the present invention is preferably a pigment multimer having a dipyrromethene structure, and the pigment site in the pigment multimer having a dipyrromethene structure is a dipyrromethene compound represented by the general formula (M) and a metal or a metal compound. It is preferable that the structure is derived from a dipyrromethene metal complex compound obtained from the above or a tautomer thereof.
Furthermore, as the dipyrromethene metal complex compound obtained from the dipyrromethene compound represented by the general formula (M) and a metal or a metal compound or a tautomer thereof, the general formula (5) or the general formula (6) may be used. The dipyrromethene metal complex compound represented is preferred.
Next, the dye multimer will be described.

The specific dye in the present invention is preferably a pigment multimer having a dipyrromethene structure, but preferably has a weight average molecular weight (Mw) of 5,000 or more and 20,000 or less, more preferably 5,000 or more and 16 or more. 2,000 or less, more preferably 6,000 or more and 12,000 or less.
When the weight average molecular weight (Mw) is less than 5,000, when a blue pixel is formed, thermal diffusion (color transfer) of the colorant due to heat treatment, penetration of the colorant, alkali elution resistance, and solvent resistance deteriorate. Tend. When the weight average molecular weight exceeds 20,000, the development residue tends to deteriorate.

Further, the dispersity (Mw / Mn) is preferably 1.00 or more and 2.50 or less.
When the dispersity (Mw / Mn) exceeds 2.50, when a colored film is formed, the thermal diffusion (color transfer) of the colorant by heat treatment, the soaking of the colorant, the alkali elution resistance, and the solvent resistance deteriorate. Tend. The dispersity (Mw / Mn) needs to be 1.00 or more and 2.50 or less, preferably 1.00 or more and 2.20 or less, more preferably 1.00 or more and 2.00 or less. is there.

  In addition, a weight average molecular weight and molecular weight distribution refer to the value measured by gel permeation chromatography (GPC) using HLC-8220GPC (developing solvent NMP, detection RI, conversion value by polystyrene) manufactured by Tosoh Corporation.

The specific dye in the invention preferably has an alkali-soluble group.
Examples of the alkali-soluble group include a carboxyl group, a phosphono group, and a sulfo group. Among these, a carboxyl group is preferable.
The acid value of the specific dye is preferably 0.5 mmol / g or more and 3.0 mmol / g or less, preferably 0.6 mmol / g or more and 2.5 mmol / g or less from the viewpoint of being suitably used in the photolithographic method described later. More preferably, it is 0.7 mmol / g or more and 2.0 mmol / g or less.

  Examples of the specific dye in the present invention include dimers, trimers, oligomers, and polymers.

When the dye multimer is synthesized by a copolymerization reaction, the other polymerizable monomer (comonomer) is not particularly limited as long as it can be polymerized with the polymerizable dye monomer.
These comonomers include styrenic compounds, carboxylic acid monomers, and their esters, amides, imides or anhydrides, and vinyl compounds.
Examples of styrenic compounds are styrene, α-methylstyrene, hydroxystyrene, p-chloromethylstyrene, and m-chloromethylstyrene.
Examples of α, β-unsaturated carboxylic acids are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and 1-butyne-2,3,4-tricarboxylic acid.

Examples of unsaturated carboxylic acid esters include the above-mentioned α, β-unsaturated carboxylic acid methyl ester, ethyl ester, 2-hydroxyethyl ester, propyl ester, butyl ester, octyl ester, dodecyl ester, 2,2, 6,6-tetramethyl-4-piperidyl ester, 1,2,2,6,6-pentamethyl-4-piperidyl ester, 2- [3- (2-benzotriazolyl) -4-hydroxyphenyl] ethyl ester It is.
Examples of unsaturated carboxylic acid amides include methyl amide, dimethyl amide, ethyl amide, diethyl amide, propyl amide, dipropyl amide, butyl amide, dibutyl amide, hexyl amide, octyl amide, phenyl of the above α, β-unsaturated carboxylic acid. Amides and the like.
Examples of unsaturated carboxylic acid imides are maleimide, itaconimide, N-butylmaleimide, N-octylmaleimide, and N-phenylmaleimide. Examples of vinyl compounds are vinyl acetate, N-vinyl carbazole, and N-vinyl pyrrolidone.

  Although the copolymerization ratio of the polymerizable dye monomer and the comonomer varies depending on the type of the polymerizable dye monomer, it is usually preferably in a ratio of 5 to 10,000 g of the comonomer with respect to 100 g of the polymerizable dye monomer. A ratio is more preferable, and a ratio of 5 to 100 g of comonomer is particularly preferable.

  The specific dye in the present invention has at least one of structural units represented by the following general formula (A), general formula (B), and general formula (C), or represented by the general formula (D) Dye multimers containing the dipyrromethene structure represented are preferred.

(Structural unit represented by formula (A))

In general formula (A), X ^A1 represents a linking group formed by polymerization, L ^A1 represents a single bond or a divalent linking group, and Dye represents one arbitrary hydrogen atom from a dye compound containing a dipyrromethene structure. Represents ˜1 + m pigment residues removed. X ^A2 represents a linking group formed by polymerization, L ^A2 represents a single bond or a divalent linking group, m represents an integer of 0 to 3, and when m is 2 or more, the structure in [] May be the same or different. Dye and LA ² may be linked by any of a covalent bond, an ionic bond, and a coordination bond.

In the general formula (A), X ^A1 and X ^A2 each independently represent a linking group formed by polymerization. That is, it refers to a portion that forms a repeating unit corresponding to the main chain formed by the polymerization reaction. Two sites represented by * are repeating units.
X ^A1 and X ^A2 each independently include a linking group formed by polymerizing a substituted or unsubstituted unsaturated ethylene group, a linking group formed by ring-opening polymerization of a cyclic ether, and the like. Is a linking group formed by polymerizing an unsaturated ethylene group. Specific examples include the following linking groups, but the linking groups formed by polymerization in the present invention are not limited to these.
In the following (X-1) to (X-15), it is connected to L ^A1 or L ^A2 at the site indicated by *.

In general formula (A), L ^A1 and L ^A2 each independently represent a single bond or a divalent linking group. L ^A1 and L ^A2 are each independently a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (for example, methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.) A substituted or unsubstituted arylene group having 6 to 30 carbon atoms (for example, a phenylene group, a naphthalene group, etc.), a substituted or unsubstituted heterocyclic linking group, —CH ₂ ═CH ₂ —, —O—, —S—. , —NR—, —C (═O) —, —SO—, —SO ₂ —, a linking group represented by the following general formula (2), a linking group represented by the following general formula (3), or the following And a linking group formed by linking two or more of these (for example, —N (R) C (═O) —, —OC (═O) —). , -C (= O) N (R)-, -C (= O) O-). R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
The divalent linking group of the present invention is not limited at all as long as the effects of the present invention can be obtained.

Here, R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ³ represents a hydrogen atom or a substituent. k represents an integer of 0 to 4, and when k is 2 or more, R ³ may be the same or different.
In the general formula (2) to the general formula (4), * represents a position bonded to the —C (R ¹ ) ═CH ₂ group in the general formula (1), and ** represents the general formula (1). It represents a position bonded with the (case of n = 0) ^{L 2} or Dye in.

In general formula (A), m represents an integer of 0 to 3. When m is 2 or more, a plurality of X ^A2 may be the same or different. Similarly, when m is 2 or more, a plurality of L ^A2 may be the same or different.
M is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

In the general formula (A), Dye represents a dye residue obtained by removing 1 to 1 + m of arbitrary hydrogen atoms of a dye compound having a dipyrromethene structure.
In General Formula (A), Dye and L ^A2 may be linked by any of a covalent bond, an ionic bond, and a coordination bond, but are preferably linked by an ionic bond or a coordination bond.

(Structural unit represented by general formula (B))

In the general formula (B), X ^B1 represents a linking group formed by polymerization, L ^B1 represents a single bond or a divalent linking group, and A represents a group capable of ionic bonding or coordination bonding with Dye. Dye represents a dye compound having a dipyrromethene structure having a group capable of ionic bonding or coordination bond with A, or a dye residue obtained by removing 1 to m arbitrary hydrogen atoms from the dye compound. X ^B2 represents a linking group formed by polymerization, L ^B2 represents a single bond or a divalent linking group, m represents an integer of 0 to 3, and when m is 2 or more, the structure in [] May be the same or different. Dye and the L ^B2, covalent bonding, ionic bonding, and may be connected at any coordination bonds.

X ^B1 , L ^B1 , and m in the general formula (B) have the same meanings as X ^A1 , L ^A1 , and m in the general formula (A), respectively, and the preferred ranges are also the same.
X ^B2 and L ^B2 in the general formula (B) have the same ^meanings as X ^A2 and L ^A2 in the general formula (A), respectively, and the preferred ranges are also the same.
The group represented by A in the general formula (B) may be any group capable of ionic bonding or coordination bonding with Dye, and the group capable of ionic bonding may be either an anionic group or a cationic group. . The anionic group is preferably an anionic group having a pKa of 12 or less, such as a carboxyl group, a phospho group, a sulfo group, an acylsulfonamide group, or a sulfonimide group, more preferably a pKa of 7 or less, still more preferably 5 or less. The anionic group may form an ionic bond or a coordinate bond with Ma or a heterocyclic group in Dye, but it is more preferable to form an ionic bond with Ma. Specific examples of preferred anionic groups are shown below, but the present invention is not limited thereto. In the following specific examples, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

  As the cationic group represented by A in the general formula (B), a substituted or unsubstituted onium cation (for example, a substituted or unsubstituted ammonium group, pyridinium group, imidazolium group, sulfonium group, phosphonium group, etc.) Are preferable, and a substituted ammonium group is particularly preferable.

In general formula (B), m represents an integer of 0 to 3. When m is 2 or more, a plurality of ^XB2 may be the same or different. Similarly, when m is 2 or more, a plurality of L ^B2 may be the same or different.
M is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

Dye in the general formula (B) is a dye compound containing a dipyrromethene structure, or a dye residue obtained by removing 1 to m arbitrary hydrogen atoms from the dye compound.
In General Formula (B), Dye and L ^B2 may be connected by any of a covalent bond, an ionic bond, and a coordinate bond, but are preferably connected by an ionic bond or a coordinate bond.

(Structural unit represented by general formula (C))

In the general formula (C), L ^C1 represents a single bond or a divalent linking group, and Dye represents a divalent dye residue obtained by removing two arbitrary hydrogen atoms from a dye compound containing a dipyrromethene structure.
L ^C1 in the general formula (C) has the same meaning as L ^A1 in the general formula (A), and the preferred range is also the same.

  Below, the structural unit containing the dipyrromethene structure which comprises specific dye is shown.

(Copolymerization component)
The specific dye of the present invention may be composed of only the structural units represented by the general formula (A), the general formula (B), and the general formula (C), but the general formula (A), At least one of the structural units represented by the general formula (B) and the general formula (C) and other structural units may be included (in this case, the general formula (A), It is preferable that at least one of the structural unit represented by the general formula (B) and the general formula (C) and at least one of the other structural units includes an alkali-soluble group.
The other structural unit is preferably a structural unit having an alkali-soluble group (carboxyl group, phosphono group, sulfo group, etc.) in the side chain.
Hereinafter, although the specific example of another structural unit is shown, this invention is not limited to these.

  Moreover, the following structural unit which has an unsaturated group in a side chain is also preferable as a copolymerization component. For example, an ethylenically unsaturated group (for example, a methacryl group, an acryl group, a styryl group, etc.) is mentioned, and heat resistance and solvent resistance are improved by including these structural units.

(Dye multimer represented by formula (D))

In General Formula (D), L ^D1 represents an m-valent linking group, m represents an integer of 2 to 100, and when m is 2 or more, the structures of Dye may be the same or different. . Dye represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye compound containing a dipyrromethene structure.
m is preferably 2 to 80, more preferably 2 to 40, and particularly preferably 2 to 10.

When m is 2, the divalent linking group represented by L ^D1 is a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (for example, methylene group, ethylene group, trimethylene group). , Propylene group, butylene group, etc.), substituted or unsubstituted arylene group having 6 to 30 carbon atoms (eg, phenylene group, naphthalene group, etc.), substituted or unsubstituted heterocyclic linking group, —CH ₂ ═CH ₂ — , —O—, —S—, —NR—, —C (═O) —, —SO—, —SO ₂ —, and a linking group formed by linking two or more thereof (for example, —N (R) C (= O)-, -OC (= O)-, -C (= O) N (R)-, -C (= O) O-, -N (R) C (= O) N (R)-etc.) are preferred. R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
The m-valent linking group in which m is 3 or more is a substituted or unsubstituted arylene group (1,3,5-phenylene group, 1,2,4-phenylene group, 1,4,5,8-naphthalene group, etc.) And a linking group formed by substituting the divalent linking group using a heterocyclic linking group (for example, 1,3,5-triazine group, etc.), an alkylene linking group or the like as a central mother nucleus.

(Dye monomer represented by general formula (1))
The specific dye monomer in the present invention is also preferably obtained by polymerizing a dye monomer containing a dipyrromethene structure represented by the following general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. L ¹ is —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ² ) —, —C (═O) O—, The group represented by (2), the group represented by the following general formula (3), or the group represented by the following general formula (4) is represented. L ² represents a divalent linking group. m and n each independently represents 0 or 1. Dye represents a dye residue containing a dipyrromethene structure. R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Here, R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ³ represents a hydrogen atom or a substituent. k represents an integer of 0 to 4, and when k is 2 or more, R ³ may be the same or different. In the general formula (2) to the general formula (4), * represents a position bonded to the —C (R ¹ ) ═CH ₂ group in the general formula (1), and ** represents the general formula (1). It represents a position bonded with the (case of n = 0) ^{L 2} or Dye in.

That is, the dye monomer containing the dipyrromethene structure represented by the general formula (1) is added to the dye compound containing the dipyrromethene structure by-(L ² ) _n- (L ¹ ) _m -C (R ¹ ) = CH. ₂ is a compound into which a polymerizable group represented by ₂ is introduced.
When both m and n are 0, a -C (R ¹ ) = CH ₂ group is directly introduced into a dye compound containing a dipyrromethene structure.

In the general formula (1), R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. When R ¹ is an alkyl group or an aryl group, it may be unsubstituted or substituted.

When R ¹ is an alkyl group, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 6 carbon atoms is preferable. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, octyl group, isopropyl group, cyclohexyl group and the like.
When R ¹ is an aryl group, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 12 carbon atoms is preferable. Examples of the aryl group include a phenyl group and a naphthyl group.

When R ¹ is a substituted alkyl group or a substituted aryl group, the substituent is a halogen atom (for example, fluorine, chlorine, bromine, iodine), an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 1 carbon atoms). 12 alkyl groups, for example, methyl, ethyl, propyl, butyl, isopropyl, t-butyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, adamantyl), aryl groups (preferably having 6 to 24 carbon atoms, more Preferably it is a C6-C12 aryl group, for example, phenyl, naphthyl), a heterocyclic group (preferably C1-C24, more preferably a C1-C12 heterocyclic group, for example, 2-thienyl. 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazoli , 1-pyrazolyl, benzotriazol-1-yl), silyl group (preferably a silyl group having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, such as trimethylsilyl, triethylsilyl, tributylsilyl, t- (Butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group, nitro group, sulfonic acid group, phosphonic acid group, carboxyl group, alkoxy group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms) And more preferably an alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy group such as cyclopentyloxy, cyclohexyl Oxy), an aryloxy group (preferably having 6 to 24 carbon atoms) More preferably, it is an aryloxy group having 6 to 12 carbon atoms, such as phenoxy or 1-naphthoxy, and a heterocyclic oxy group (preferably having 1 to 24 carbon atoms, more preferably a heterocyclic oxy group having 1 to 12 carbon atoms). , For example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), a silyloxy group (preferably a silyloxy group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, for example, trimethylsilyloxy, t -Butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably an acyloxy group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), Alkoxycarbonyloxy group (preferably having 2 carbon atoms) 24, more preferably an alkoxycarbonyloxy group having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, such as ethoxycarbonyloxy, t-butoxycarbonyloxy), cycloalkyloxycarbonyloxy (for example, cyclohexyloxycarbonyl) Oxy)), aryloxycarbonyloxy group (preferably aryloxycarbonyloxy group having 7 to 24 carbon atoms, more preferably 7 to 12 carbon atoms, such as phenoxycarbonyloxy), carbamoyloxy group (preferably having 1 carbon atom) To 24, more preferably a carbamoyloxy group having 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N- Ethyl-N- Phenylcarbamoyloxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, for example, N, N- Diethylsulfamoyloxy, N-propylsulfamoyloxy), an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms). For example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), arylsulfonyloxy groups (preferably arylsulfonyloxy groups having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, such as phenylsulfonyl Oxy), an acyl group (preferably having 1 to 2 carbon atoms) , More preferably an acyl group having 1 to 12 carbon atoms, such as formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl)

An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl ), An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 12 carbon atoms, such as phenoxycarbonyl), a carbamoyl group (preferably having 1 to 24 carbon atoms, more preferably A carbamoyl group having 1 to 12 carbon atoms such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methyl − -Phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), an amino group (preferably an amino group having 24 or less carbon atoms, more preferably 12 or less carbon atoms, such as amino, methylamino, N, N-dibutylamino, Tetradecylamino, 2-ethylhexylamino, cyclohexylamino), anilino group (preferably an anilino group having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, such as anilino, N-methylanilino), heterocyclic amino A group (preferably a C1-C24, more preferably a C1-C12 heterocyclic amino group such as 4-pyridylamino), a carbonamido group (preferably C2-C24, more preferably C2 ~ 12 carbonamido groups such as acetamide, benzamide, tetradecanamide, (Roylamide, cyclohexaneamide), ureido group (preferably a ureido group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as ureido, N, N-dimethylureido, N-phenylureido), imide group ( Preferably, it is an imide group having 20 or less carbon atoms, more preferably 12 or less carbon atoms, for example, N-succinimide, N-phthalimide), alkoxycarbonylamino group (preferably having 2 to 24 carbon atoms, more preferably 2 carbon atoms). -12 alkoxycarbonylamino group, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 24 carbon atoms, Better Preferably, it is an aryloxycarbonylamino group having 7 to 12 carbon atoms, such as phenoxycarbonylamino), a sulfonamide group (preferably a sulfonamide group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, Methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexanesulfonamide), sulfamoylamino group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms). And, for example, N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably an azo group having 1 to 24 carbon atoms, more preferably 1 to 24 carbon atoms). For example, phenylazo, 3-pyrazolylazo), alkylthio group (preferably Or an alkylthio group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms such as methylthio, ethylthio, octylthio, cyclohexylthio), an arylthio group (preferably having 6 to 24 carbon atoms, more preferably 6 carbon atoms). An arylthio group having ˜12, for example, phenylthio), a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as 2-benzothiazolylthio, 2 -Pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 24 carbon atoms, more preferably an alkylsulfinyl group having 1 to 12 carbon atoms, for example, dodecanesulfinyl),

An arylsulfinyl group (preferably an arylsulfinyl group having 6 to 24 carbon atoms, more preferably an arylsulfinyl group having 6 to 12 carbon atoms, for example, phenylsulfinyl), an alkylsulfonyl group (preferably having 1 to 24 carbon atoms, more preferably 1 carbon atom) -12 alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl groups (preferably having 6 carbon atoms) To 24, more preferably an arylsulfonyl group having 6 to 12 carbon atoms, for example, phenylsulfonyl, 1-naphthylsulfonyl), sulfamoyl group (preferably having 24 or less carbon atoms, more preferably carbon 16 or less sulfamoyl groups, for example, sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), A sulfo group, a phosphonyl group (preferably a phosphonyl group having 1 to 24 carbon atoms, more preferably a phosphonyl group having 1 to 12 carbon atoms, such as phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), a phosphinoylamino group (preferably Is a phosphinoylamino group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and examples thereof include diethoxyphosphinoylamino and dioctyloxyphosphinoylamino).

  Among the above substituents, halogen atom, alkyl group, aryl group, hydroxyl group, sulfonic acid group, phosphonic acid group, carboxylic acid group, alkoxy group, aryloxy group, alkoxycarbonyloxy group, cycloalkylcarbonyloxy group, aryl Oxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carbonamido group, imide group, sulfonamido group , Sulfamoylamino group, sulfamoyl group are preferable, alkyl group, aryl group, hydroxyl group, sulfonic acid group, phosphonic acid group, carboxylic acid group, alkoxy group, aryloxy group, alkoxycarbonyloxy , Aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carbonamido group, sulfonamido group, A sulfamoylamino group and a sulfamoyl group are more preferable, and a hydroxyl group, a sulfonic acid group, a phosphonic acid group, a carboxylic acid group, an alkoxy group, an aryloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, a sulfo group. More preferred are a famoyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Group, a carboxylic acid group, an alkoxy group, an alkoxycarbonyl group, a carbamoyloxy group, a sulfamoylamino group, an alkylsulfonyloxy group, an acyl group, an alkoxycarbonyl group is particularly preferred.

  Among the above particularly preferred substituents, a sulfonic acid group, a carboxylic acid group, an alkoxy group, an alkoxycarbonyloxy group, an alkylsulfonyloxy group, and an alkoxycarbonyl group are more preferable, and a sulfonic acid group, a carboxylic acid group, an alkoxy group, and an alkoxycarbonyl group. A group is more preferable, and a sulfonic acid group, a carboxylic acid group, and an alkoxy group are particularly preferable.

In the general formula (1), R ¹ is preferably a hydrogen atom, an alkyl group or an aryl group, particularly preferably a hydrogen atom or an alkyl group.

In the general formula (1), when the substituents of the substituted alkyl group and the substituted aryl group of R ¹ are further substitutable groups, the substituents described above may be substituted. When substituted with the above substituents, these substituents may be the same or different.

In the general formula (1), L ¹ represents —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ² ) —, —C (= O) represents O—, a group represented by the following general formula (2), a group represented by the general formula (3), or a group represented by the general formula (4). Here, R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

In the general formula (1), the alkyl group, aryl group, and heterocyclic group represented by R ² are the alkyl group, aryl group, and heterocyclic group described above for the substituted alkyl group and substituted aryl group represented by R ^1. Is given as an example, and the preferred embodiment is also the same.
The alkyl group, aryl group, and heterocyclic group of R ² may be substituted with the substituent described in the above R ¹ , and when they are substituted with two or more substituents, their substitution The groups may be the same or different.

Below, in the general formula (1), is represented by groups represented by the following formula represented by L ¹ (2), a group represented by the general formula (3), and general formula (4) The group will be described.

Here, R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, R ³ represents a hydrogen atom or a substituent, k represents an integer of 0 to 4, and k is 2 In these cases, R ³ may be the same or different. * Represents the position bonded to the —C (R ¹ ) ═CH ₂ group in the general formula (1), and ** represents L ² or Dye (in the case of n = 0) in the general formula (1). Represents the position to join.

R ² has the same meaning as R ² described in the general formula (1), and the preferred embodiment is also the same.

R ³ represents a hydrogen atom or a substituent, and examples of the substituent represented by R ³ include the substituents described for the substituted alkyl group and substituted aryl group of R ¹ , and preferred embodiments are also the same. It is. k represents 0, 1, 2, 3, 4; When k is 2, 3, or 4, R ³ may be the same or different.
When the substituent of R ³ is a further substitutable group, it may be substituted with the substituent described in the above R ¹ , and when it is substituted with two or more substituents These substituents may be the same or different.

As L ¹ , from the viewpoint of synthesis, —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ² ) —, —C (= O) O- are preferable, -OC (= O) -, - C (= O) N (R 2) -, - C (= O) O- , more preferably, -C (= O) N ( R 2 )-And -C (= O) O- are more preferable.

Next, L ² in the general formula (1) will be described.
L ² represents a divalent linking group that links L ¹ or —C (R ¹ ) ═CH ₂ group (when m = 0) and Dye.
L ² is preferably an alkylene group, an aralkylene group, an arylene group, —O—, —C (═O) —, —OC (═O) —, OC (═O) O—, —OSO ₂ —, ^{-OC (= O) N (R} 50) -, - N (R 50) -, - N (R 50) C (= O) -, - N (R 50) C (= O) O -, - N (R ⁵⁰ ) C (═O) N (R ⁵¹ ) —, —N (R ⁵⁰ ) SO ₂ —, —N (R ⁵⁰ ) SO ₂ N (R ⁵¹ ) —, —S—, —S—S— _{, -SO -, - SO 2 -} , - SO 2 N (R 50) -, - SO 2 O- and the like. In addition, a plurality of the above divalent linking groups may be bonded to form a new divalent linking group.

R ⁵⁰ and R ⁵¹ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Examples of the alkyl group, aryl group, and heterocyclic group of R ⁵⁰ and R ⁵¹ include the alkyl group, aryl group, and heterocyclic group described above for the substituent of R ¹ , and preferred embodiments are also the same. The alkyl group, aryl group, and heterocyclic group of R ⁵⁰ and R ⁵¹ may be substituted with the substituents described for the substituent of R ¹ , or may be substituted with two or more substituents. These substituents may be the same or different.

When L ² is an alkylene group, an aralkylene group, or an arylene group, it may be unsubstituted or substituted, and when it is substituted, it is substituted with the substituent described for the substituent of R ^1. When it is substituted with two or more substituents, these substituents may be the same or different.
When L ² is an alkylene group, an aralkylene group, or an arylene group, an alkylene group having 1 to 12 carbon atoms, an aralkylene group having 6 to 18 carbon atoms, or an arylene group having 6 to 18 carbon atoms is preferable. An alkylene group having 8 to 8 carbon atoms, an aralkylene group having 6 to 16 carbon atoms and an arylene group having 6 to 12 carbon atoms are more preferable, and an alkylene group having 1 to 6 carbon atoms and an aralkylene group having 6 to 12 carbon atoms are still more preferable.

As the combination of L ¹ and L ² , L ¹ is —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ² ) —, — C (= O) O-, L ² is an alkylene group having 1 to 12 carbon atoms, an aralkylene group having 6 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, an alkylthioether having 2 to 18 carbon atoms, a carbon number Preferred are an alkylcarbonamide group having 2 to 18 carbon atoms and an alkylaminocarbonyl group having 2 to 18 carbon atoms. More preferably, L ¹ is —OC (═O) —, —C (═O) N (R ² ) —, —C (═O) O—, and L ² is an alkylene group having 1 to 8 carbon atoms, Embodiments of an aralkylene group having 6 to 16 carbon atoms, an arylene group having 6 to 12 carbon atoms, an alkylthioether having 2 to 12 carbon atoms, an alkylcarbonamide group having 2 to 12 carbon atoms, and an alkylaminocarbonyl group having 2 to 12 carbon atoms More preferably, L ¹ is —C (═O) N (R ² ) — or —C (═O) O—, L ² is an alkylene group having 1 to 6 carbon atoms, or 6 to 12 carbon atoms. Are an aralkylene group, an alkylthioether having 2 to 6 carbon atoms, an alkylcarbonamide group having 2 to 6 carbon atoms, and an alkylaminocarbonyl group having 2 to 6 carbon atoms.

Below, in the general formula (1) in ^{_{- (L 2) n - (}} L 1) m -C (R 1) = examples of the polymerizable group represented by CH _2. However, the present invention is not limited to these.

(Exemplary compounds of specific dyes)
Hereinafter, although the exemplary compound of the specific dye in this invention is shown, this invention is not limited to the following exemplary compounds at all.
In the following exemplary compounds, “wt-%” is based on mass.
Moreover, in exemplary compound 2-1 to 2-5, it superposes | polymerizes according to the ratio which shows the structural component which comprises the composition ratio a, and the methacrylic acid component corresponded to composition ratio (b + c) in a table | surface. A part of the methacrylic acid component of the dye multimer generated by polymerization is coordinated with Zn by an equimolar amount with respect to the component constituting the composition ratio a.

(Synthesis example of specific dye)
Hereinafter, examples of the synthesis method will be shown for some specific examples of the specific dye, but the present invention is not limited thereto.

-Synthesis of Exemplified Compound 1-4-
The following dye monomer 1 (5.0 g), methacrylic acid (0.68 g) and 240 mg of n-dodecanethiol as a chain transfer agent were dissolved in 32 ml of propylene glycol monomethyl ether acetate (PGMEA) and stirred at 85 ° C. under nitrogen. Then, 542 mg of dimethyl 2,2′-azobis (2-methylpropionate) was added. Thereafter, 240 mg of dimethyl 2,2′-azobis (2-methylpropionate) was additionally added twice every 2 hours, the temperature was raised to 90 ° C., and the mixture was further stirred for 2 hours. After completion of the reaction, the reaction solution was dropped into 400 ml of acetonitrile, and the resulting crystal was filtered to obtain Exemplified Compound 1-4 (4.8 g).
The following dye monomer 1 can be synthesized, for example, according to the synthesis method described in JP-A-2008-292970.
In addition, the weight average molecular weight can be adjusted by increasing / decreasing the amount of chain transfer agent and the reaction temperature, and the degree of dispersion can be adjusted by changing the type / amount of reprecipitation solvent.

-Synthesis of Exemplified Compound 2-3-
The following dye monomer 2 (20 g), methacrylic acid (5.88 g) and 520 mg of thiomalic acid as a chain transfer agent were dissolved in 150 ml of propylene glycol monomethyl ether (PGME), stirred at 85 ° C. under nitrogen, dimethyl 2, 1.2 g of 2′-azobis (2-methylpropionate) was added. Thereafter, 1.2 g of dimethyl 2,2′-azobis (2-methylpropionate) was additionally added twice every 2 hours, the temperature was raised to 90 ° C., and the mixture was further stirred for 2 hours. After completion of the reaction, the reaction solution was dropped into 2000 ml of acetonitrile, and the resulting crystal was filtered to obtain Exemplary Compound 2-3 (21.2 g). ^{Since the} AcO proton peak disappeared from the ¹ H NMR spectrum, it was confirmed that the main chain carboxylic acid was coordinated as in Example Compound 2-3.
The following dye monomer 2 can also be synthesized according to, for example, the synthesis method described in JP-A-2008-292970. In addition, the weight average molecular weight can be adjusted by increasing / decreasing the amount of chain transfer agent and the reaction temperature, and the degree of dispersion can be adjusted by changing the type / amount of reprecipitation solvent.

  As mentioned above, although the specific dye in this invention was demonstrated, it is preferable to use 1 type of specific dye for the blue pixel of the color filter of this invention, and may use 2 or more types.

The content ratio of the blue colorant to the purple colorant in the blue colored radiation-sensitive composition is preferably blue colorant: purple colorant = 80: 20 to 60:40 on a mass basis. 70:30 is particularly preferable.
The content of the total colorant in the blue colored radiation-sensitive composition is preferably 10% to 40% on a mass basis with respect to the total solid content of the blue colored radiation-sensitive composition. More preferably, it is 20% to 30%.

  In addition, as the colorant, a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azoic dye, a disperse dye, an oil-soluble dye, a food dye, and / or a derivative thereof can also be used. .

  Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Solvent orange 45; Rhodamine B, Rhodamine 110 and other acid dyes and derivatives of these dyes are also preferably used.

Among them, as the dye, triallylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazoleazo The dye is preferably selected from anilinoazo, pyrazolotriazole azo, pyridone azo, anthrapyridone, and pyromethene.
The dye may be a multimer.

  Furthermore, the color filter constituted by using the colored radiation-sensitive composition of the present invention includes not only three primary color filters of green, red, and blue, but also six colors including complementary colors of cyan, yellow, and magenta. The present invention is also effective in a color filter or a multi-color filter such as a four-color filter in which cyan and colorless are added to the three primary colors.

  Considering that the color filter obtained by applying the colored radiation-sensitive composition of the present invention preferably has high color purity as the pigment applied to the colored radiation-sensitive composition of the present invention. A fine one is preferred. In consideration of the handling properties of the colored radiation-sensitive composition, the average primary particle diameter of the pigment is preferably 5 nm to 100 nm, and more preferably 5 nm to 50 nm.

  In the colored radiation-sensitive composition of each color, by adjusting the content of the colorant to the respective ranges described above, an appropriate chromaticity can be obtained when a color filter is produced from the colored radiation-sensitive composition. It is done. Further, since radiation curing is sufficiently advanced and the strength as a colored cured film can be maintained, it is possible to prevent the development latitude during alkali development from becoming narrow.

When the pigment is used as the colorant (A) in the colored radiation-sensitive composition of the present invention, the pigment is dispersed together with a pigment dispersant, an organic solvent, a pigment derivative, and other components, if necessary. A pigment dispersion is prepared, and the resulting pigment dispersion is prepared by mixing with (B) a specific resin, (C) a polymerizable compound, (D) an ultraviolet absorber, and other components added as necessary. preferable.
The composition of the pigment dispersion and the method for preparing the pigment dispersion are described in detail below.

In the present invention, a pigment dispersion may be prepared separately for each pigment, or two, three, or four or more may be combined to prepare a pigment dispersion.
When two or more pigment dispersions are used, the composition other than the pigment in the pigment dispersion and the method for preparing the pigment dispersion may be the same or different.

  The method for preparing the pigment dispersion is not particularly limited, and as a dispersion method, for example, a pigment and a pigment dispersant are mixed in advance and dispersed in advance using a homogenizer or the like, using zirconia beads or the like. It can be carried out by finely dispersing using a bead disperser (for example, a disperse mat manufactured by GETZMANN).

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

  Examples of the terminal-modified polymer having an anchor site to the pigment surface include polymers having a phosphate group at the terminal described in JP-A-3-112992, JP-T2003-533455, and the like. Examples thereof include a polymer having a sulfonic acid group at the terminal end described in JP-A-273191, and a polymer having a partial skeleton of an organic dye or a heterocyclic ring described in JP-A-9-77994. In addition, a polymer in which two or more anchor sites (acid group, basic group, partial skeleton of organic dye, heterocycle, etc.) to the surface of the pigment described in JP-A-2007-277514 are introduced. It is preferable because of excellent dispersion stability.

  Examples of the graft polymer having an anchor site to the pigment surface include poly (lower alkyleneimine) described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, and the like. ) And a polyester reaction product, a reaction product of polyallylamine and polyester described in JP-A-9-169821, etc., a macromonomer described in JP-A-10-339949, JP-A-2004-37986, and the like, Copolymers with nitrogen atom monomers, graft-type polymers having partial skeletons or heterocyclic rings of organic dyes described in JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, etc. And a copolymer of a macromonomer and an acid group-containing monomer described in JP2010-106268A. It is. In particular, the amphoteric dispersion resin having a basic group and an acidic group described in JP 2009-203462 A is from the viewpoint of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the colored radiation-sensitive composition. Particularly preferred.

  As the macromonomer used when the graft polymer having an anchor site to the pigment surface is produced by radical polymerization, a known macromonomer can be used. Macromonomer AA-6 (terminal) manufactured by Toa Gosei Co., Ltd. Polymethyl methacrylate whose group is a methacryloyl group), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 ( Polybutyl acrylate whose end group is a methacryloyl group), PLACEL FM5 manufactured by Daicel Chemical Industries, Ltd. (5 molar equivalent addition product of ε-caprolactone of 2-hydroxyethyl methacrylate), FA10L (2-hydroxyethyl acrylate) ε-caprolactone 10 molar equivalent addition product), and JP-A-2-2720 Polyester macromonomer described in No. 09 publication. Among these, the polyester-based macromonomer that is particularly excellent in flexibility and solvophilicity is from the viewpoint of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the colored radiation-sensitive composition using the pigment dispersion. In particular, a polyester macromonomer represented by a polyester macromonomer described in JP-A-2-272009 is most preferable.

  As the block polymer having an anchor site to the pigment surface, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.

  The pigment dispersant that can be used in the present invention is also available as a commercial product, and specific examples thereof include “Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester)”, 110 (by BYK Chemie). Copolymer containing acid groups), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ) "EFKA 4047, 4050-4010-4165 (polyurethane)", EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylic acid) Salt), 6220 (fatty acid polyester), 6745 Phthalocyanine derivatives), 6750 (azo pigment derivatives) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co.,“ Polyflow No. 50E, No. .300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA-703-50, manufactured by Enomoto Kasei Co., Ltd. DA-705, DA-725 "," Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "manufactured by Kao Corporation," Homogenol L- 18 (polymer polycarboxylic acid) "," Emulgen 920, 930, 935, 85 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine) ”manufactured by Nippon Lubrizol Co., Ltd. , 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX, manufactured by Nikko Chemical Co., Ltd. ” (Polyoxyethylene monostearate), Kawaken Fine Chemical Co., Ltd. Hinoact T-8000E, Shin-Etsu Chemical Co., Ltd., Organosiloxane Polymer KP341, Yusho Co., Ltd. “W001: Cationic System Surfactant ", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester Nonionic surfactants such as, anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, manufactured by Morishita Sangyo Co., Ltd.” EFKA Polymer 401, EFKA Polymer 450 ”,“ Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid manufactured by San Nopco Corporation Polymeric dispersants such as “100”, “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121 manufactured by ADEKA Corporation , P-123 ”, Sanyo Chemical Co., Ltd.“ Ionette S-20 ”, Nippon Shokubai Co., Ltd.“ Acryure RD-F8 ”, Fujikura Kasei Co., Ltd.“ Acrybase FFS-6824 ”, and the like.

  These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant. The pigment dispersant in the present invention is preferably a terminal-modified polymer, a graft polymer, or a block polymer having an anchor site to the pigment surface.

As content of the pigment dispersant in a pigment dispersion liquid, it is preferable that it is 1-80 mass parts with respect to 100 mass parts of pigments, 5-70 mass parts is more preferable, and it is 10-60 mass parts. Further preferred.
Specifically, if a polymer dispersant is used, the amount used is preferably in the range of 5 to 100 parts in terms of mass, and in the range of 10 to 80 parts, with respect to 100 parts by mass of the pigment. It is more preferable.

<Pigment derivative>
The pigment dispersion preferably further contains a pigment derivative.
The pigment derivative is a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group. The pigment derivative preferably contains a pigment derivative having an acidic group or a basic group from the viewpoint of dispersibility and dispersion stability.

Examples of the organic pigment for constituting the pigment derivative include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.
Moreover, as an acidic group which a pigment derivative has, a sulfonic acid, carboxylic acid, and its quaternary ammonium salt are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is especially preferable. The basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group.

  As the pigment derivative, quinoline-based, benzimidazolone-based and isoindoline-based pigment derivatives are particularly preferable, and quinoline-based and benzimidazolone-based pigment derivatives are more preferable. In particular, a pigment derivative having a structure represented by the following general formula (P) is preferable.

In the general formula (P), A represents a partial structure selected from the following general formulas (PA-1) to (PA-3). B represents a single bond or a (t + 1) -valent linking group. C represents a single _{bond, -NH -, - CONH -,} - CO 2 -, - SO 2 NH -, - O -, - S- or -SO ₂ - represents a. D represents a single bond, an alkylene group, a cycloalkylene group or an arylene group. E _represents -SO 3 H, -CO ₂ H or -N (Rpa) (Rpb). Rpa and Rpb each independently represents an alkyl group, a cycloalkyl group or an aryl group, and Rpa and Rpb may be linked to each other to form a ring. t represents an integer of 1 to 5.

In general formulas (PA-1) and (PA-2), R _p1 represents an alkyl group having 1 to 5 carbon atoms or an aryl group. In General Formula (PA-3), R _p2 represents a hydrogen atom, a halogen atom, an alkyl group, or a hydroxyl group. s represents the integer of 1-4. In general formula (PA-1) and general formula (PA-3), R _p3 represents a single bond, —NH—, —CONH—, —CO ₂ —, —SO ₂ NH—, —O—, —S—. or -SO ₂ - represents a. * Represents a connecting portion with B.

In general formula (P), R _p1 is particularly preferably a methyl group or a phenyl group, and most preferably a methyl group. In general formula (PA-3), R _p2 is preferably a hydrogen atom or a halogen atom, and most preferably a hydrogen atom or a chlorine atom.

  In the general formula (P), examples of the (t + 1) -valent linking group represented by B include an alkylene group, a cycloalkylene group, an arylene group, and a heteroarylene group. Among these, the linking groups represented by the following structural formulas (PA-4) to (PA-9) are particularly preferable.

  Among structural formulas (PA-4) to (PA-9), in particular, a pigment derivative having a linking group represented by the structural formula (PA-5) or (PA-8) as B is more excellent in dispersibility. This is preferable.

  In the general formula (P), examples of the alkylene group, cycloalkylene group and arylene group represented by D include methylene, ethylene, propylene, butylene, pentylene, hexylene, decylene, cyclopropylene, cyclobutylene, cyclopentylene, Examples include cyclohexylene, cyclooctylene, cyclodecylene, phenylene, naphthylene, and the like. Among these, as D, an alkylene group is particularly preferable, and alkylene having 1 to 5 carbon atoms is most preferable.

  In the general formula (P), when E represents -N (Rpa) (Rpb), examples of the alkyl group, cycloalkyl group and aryl group in Rpa and Rpb include methyl, ethyl, propyl, isopropyl, butyl, Examples include sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, octyl, decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, phenyl, naphthyl, and the like. As Rpa and Rpb, an alkyl group is particularly preferable, and an alkyl group having 1 to 5 carbon atoms is most preferable. The t is preferably 1 or 2.

1-50 mass% is preferable with respect to the total mass of a pigment, and, as for content of the pigment derivative in a pigment dispersion, 3-30 mass% is more preferable. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.
Moreover, when using together a pigment derivative, it is preferable that it is in the range of 1-30 parts in conversion of mass as a usage-amount of a pigment derivative, and is in the range of 3-20 parts with respect to 100 mass parts of pigments. A range of 5 to 15 parts is particularly preferable.

(Organic solvent)
The pigment dispersion preferably contains an organic solvent.
The organic solvent is selected depending on the solubility of each component contained in the pigment dispersion and the coating properties when the pigment dispersion is applied to a colored radiation-sensitive composition. Examples of the organic solvent that can be used in the pigment dispersion include those described later as the (E) organic solvent.
As content of the organic solvent in a pigment dispersion liquid, 50-95 mass% is preferable, and 70-90 mass% is more preferable.

(Polymer material)
The pigment dispersion is different from the specific resin (B) from the viewpoint of improving the dispersion stability, developing property control when the pigment dispersion is applied to the colored radiation-sensitive composition, in addition to the above-described components. You may further contain the polymeric material of the other structure of a structure.

Examples of the polymer material having a structure different from that of the specific resin include, for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) Acrylate, (meth) acrylic copolymer (in particular, (meth) acrylic acid copolymer containing a carboxylic acid group and a polymerizable group in the side chain is preferable), naphthalenesulfonic acid formalin condensate and the like. . Such a polymer material is adsorbed on the surface of the pigment and acts to prevent re-aggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the pigment surface are used. Preferable examples include a graft copolymer including a monomer containing a heterocyclic ring and a polymerizable oligomer having an ethylenically unsaturated bond as a copolymer unit.
Examples of other polymer materials include polyamidoamine phosphate, high molecular weight unsaturated polycarboxylic acid, polyether ester, aromatic sulfonic acid formalin polycondensate, polyoxyethylene nonyl phenyl ether, polyester amine, polyoxy Examples include ethylene sorbitan monooleate polyoxyethylene monostearate.

These polymer materials having other structures may be used alone or in combination of two or more.
As content of the polymeric material of the other structure in a pigment dispersion liquid, 20-80 mass% is preferable with respect to a pigment, 30-70 mass% is more preferable, 40-60 mass% is still more preferable.

<(B) Acrylic resin having a partial structure represented by formula (I)>
The colored radiation-sensitive composition of the present invention contains (B) an acrylic resin (specific resin) having a partial structure represented by the following formula (I).

  In formula (I), R represents a hydrogen atom or a monovalent substituent. * Represents the site of binding to the main chain structure.

  The specific resin only needs to have a partial structure represented by the formula (I), and may be obtained by polymerizing an acrylic monomer having a partial structure represented by the formula (I) alone. An acrylic resin obtained by copolymerizing a polymerizable unsaturated compound having a partial structure represented by the above and another acrylic monomer may be used. Moreover, the acrylic resin which combined the reactive compound which has the partial structure represented by Formula (I) with the side chain by the polymer reaction to the acrylic resin may be sufficient.

Examples of the unsaturated compound having a partial structure represented by the formula (I) include an unsaturated group such as a vinyl group, a (meth) acryloyloxy group, a (meth) acryl group, directly or via a linking group. And compounds bonded to the * moiety of I).
Examples of the linking group include an alkylene group having 1 to 10 carbon atoms, a phenylene group, a tolylene group, and a naphthylene group. Preferred examples of the linking group include a single bond, a methylene group, an ethylene group, a propylene group, and a phenylene group.

Examples of unsaturated compounds having a partial structure represented by formula (I) include vinylureylene benzimidazole, allyl ureylene benzimidazole (meth) acryloyloxyureylene benzimidazole, and (meth) acryloyloxy. Examples include methylureylene benzimidazole, (meth) acryloyloxyethylureylene benzimidazole, and (meth) acryloyloxyphenylureylene benzimidazole.
Of these, (meth) acryloyloxyethylureylenebenzimidazole is preferable.
As the acrylic monomer having a partial structure represented by the formula (I), a compound having a (meth) acryloyloxy group as an unsaturated group among the unsaturated compounds having the partial structure represented by the formula (I). Is mentioned.

The specific resin of the present invention may further contain a copolymer component other than the unsaturated compound having a partial structure represented by the formula (I), and is described below.
The copolymer component other than the unsaturated compound having a partial structure represented by the formula (I) that may be contained in the specific resin of the present invention is selected from the group consisting of an active methylene group and an active methine group, for example. An unsaturated compound having at least one group.
The unsaturated compound having at least one group selected from the group consisting of an active methylene group and an active methine group is a compound represented by the following formulas (B-1) and (B-2).

(In formulas (B-1) and (B-2), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may contain a hetero atom. R ² represents a single bond or 1 carbon atom. And R ³ represents a divalent group represented by any one of the following formulas (1-1) to (1-3), and R ⁴ represents a formula (1- 4) to (1-7) represents a group, and X represents a divalent group represented by any of the following formulas (1-8) to (1-10): R ⁵ Is the same as R ¹ described above.

R ¹ and R ⁵ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, a methoxy group, an ethoxy group, a propoxy group, a hexoxy group, a cyclohexoxy group, 1-11) to groups represented by (1-13), more preferably a hydrogen atom or a methyl group.

R ² is preferably a single bond, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a cyclohexylene group, an octylene group, a decylene group, or a dodecylene group, more preferably a single bond, a methylene group, or ethylene. It is a group.

  Specific examples of the compound represented by the formula (B-1) include the following compounds.

  Specific examples of the compound represented by the formula (B-2) include the following compounds.

  Compounds (I-1) to (I-7), (I-16), (II-1), (II-2) and (II-5) are compounds that lead to a structural unit consisting of a methacryl group. Moreover, the compound which derives | leads-out the structural unit which consists of an acrylic group can also be mentioned.

  Among these, a compound represented by 2- (methacryloyloxy) ethyl acetoacetate (the following (B-3)) is preferable.

  When the specific resin of the present invention contains a repeating unit derived from an unsaturated compound having at least one group selected from the group consisting of an active methylene group and an active methine group, the solvent resistance and developability are improved. The content of the repeating unit derived from the unsaturated compound having at least one group selected from the group consisting of an active methylene group and an active methine group is not particularly limited, but is all repeating contained in the specific resin of the present invention. When the unit is 100 mol%, the repeating unit represented by any one of the general formulas (B-1) and (B-2) is preferably contained in an amount of 5 mol% or more, preferably 10 mol% to 40 mol%. It is more preferable to contain.

  As a copolymerization component other than the unsaturated compound having a partial structure represented by the formula (I), which may be contained in the specific resin of the present invention, further from the following formulas (B-4) and (B-5): Mention may be made of at least one repeating unit selected.

In the above formulas (B-4) and (B-5), R ^{1 to} R ⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ¹ and X ² each independently represent — CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group, L ¹ and L ² are each independently a single bond or a divalent organic linkage. A ¹ and A ² each independently represents a monovalent organic group, m and n each independently represents an integer of 2 to 8, p and q each independently represents 1 Represents an integer of ~ 100.

R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group is preferable. As an alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.
When the alkyl group has a substituent, examples of the substituent include a hydroxy group, an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), a methoxy group, an ethoxy group, Examples include a cyclohexyloxy group.
Specific examples of preferred alkyl groups include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, A 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2-methoxyethyl group are exemplified.
R ¹ , R ² , R ⁴ , and R ⁵ are preferably hydrogen atoms, and R ³ and R ⁶ are most preferably hydrogen atoms or methyl groups from the viewpoint of adsorption efficiency on the pigment surface.

X ¹ and X ² each independently represent —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group. Among them, —C (═O) O—, —CONH—, and a phenylene group are preferable from the viewpoint of adsorptivity to the pigment, and —C (═O) O— is most preferable.

L ¹ and L ² each independently represents a single bond or a divalent organic linking group. The divalent organic linking group is preferably a substituted or unsubstituted alkylene group or a divalent organic linking group comprising the alkylene group and a hetero atom or a partial structure containing a hetero atom. Here, the alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms. In addition, examples of the hetero atom in the partial structure containing a hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom, and among them, an oxygen atom and a nitrogen atom are preferable.
Specific examples of preferable alkylene groups include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
When the alkylene group has a substituent, examples of the substituent include a hydroxy group.
The divalent organic linking group includes a heteroatom or a heteroatom selected from —C (═O) —, —OC (═O) —, and —NHC (═O) — at the end of the above alkylene group. A compound having a partial structure and linked to an adjacent oxygen atom via the heteroatom or a partial structure containing a heteroatom is preferable from the viewpoint of adsorptivity to the pigment. Here, the adjacent oxygen atom means an oxygen atom that is bonded to L ¹ in the general formula (I) and L ² in the general formula (II) on the side chain end side.

A ¹ and A ² each independently represents a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is preferable.
Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy , Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N '-Arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-aryluree Id group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl- N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group , Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group An alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkyl Sulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), Alkyl phosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate) Group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (— OPO _{3 (aryl) 2),} alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )) Monoalkyl phosphono group _(-OPO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugate Examples thereof include a base group (hereinafter referred to as an arylphosphonatoxy group), a cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, and a silyl group. Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.
Examples of the substituent include an alkoxy group, aryloxy group, alkylthio group, arylthio group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, aryl group, hetero An aryl group, an alkenyl group, an alkynyl group, and a silyl group are preferable from the viewpoint of dispersion stability.

  Specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxy Phenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, Ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group It can be exemplified phosphonophenyl phenyl group.

As A ¹ and A ² , from the viewpoint of dispersion stability and developability, a straight chain having 1 to 20 carbon atoms, a branched structure having 3 to 20 carbon atoms, and a number having 5 to 20 carbon atoms Cyclic alkyl groups are preferable, linear alkyl groups having 4 to 15 carbon atoms, branched alkyl groups having 4 to 15 carbon atoms, and cyclic alkyl groups having 6 to 10 carbon atoms are more preferable. Even more preferred are linear alkyl groups of 6 to 10 and branched alkyl groups of 6 to 12 carbon atoms.

  m and n each independently represents an integer of 2 to 8. In view of dispersion stability and developability, 4 to 6 is preferable, and 5 is most preferable.

  p and q each independently represent an integer of 1 to 100. Two or more different p and different q may be mixed. p and q are preferably 5 to 60, more preferably 5 to 40, and still more preferably 5 to 20 from the viewpoints of dispersion stability and developability.

  As specific resin in this invention, the thing containing the repeating unit represented by the said general formula (B-4) from the point of dispersion stability is preferable.

  The repeating unit represented by the formula (B-4) is more preferably a repeating unit represented by the following formula (B-6).

In the above formula (B-6), R ^{1 to} R ³ each independently represents a hydrogen atom or a monovalent organic group, La represents an alkylene group having 2 to 10 carbon atoms, and Lb represents — C (═O) — or —NHC (═O) —, A ¹ represents a monovalent organic group, m represents an integer of 2 to 8, and p represents an integer of 1 to 100. Represent.

  The repeating units represented by formula (B-1), (B-2), or (B-6) are represented by the following formulas (B-7), (B-8), or (B-9), respectively. ) Is introduced as a repeating unit of the specific resin by polymerization or copolymerization.

In the above formulas (B-7) to (B-9), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent organic group, and X ¹ and X ² are each independently- CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group, L ¹ and L ² are each independently a single bond or a divalent organic linkage. Represents a group, La represents an alkylene group having 2 to 10 carbon atoms, Lb represents -C (= O)-, or -NHC (= O)-, and A ¹ and A ² are each independently Represents a monovalent organic group, m and n each independently represents an integer of 2 to 8, and p and q each independently represents an integer of 1 to 100.

  Specific preferred examples of the monomers represented by formulas (B-7) to (B-9) [Monomers (A-1) to (A-23)] are listed below, but the present invention is as follows. Is not limited to these.

  The content of the repeating unit represented by any one of the formulas (B-4) and (B-5) is not particularly limited, but the total repeating unit contained in the specific resin of the present invention is 100 mol%. In this case, the repeating unit represented by any one of the formulas (B-4) and (B-5) is preferably contained in an amount of 30 mol% or more, more preferably 40 mol%, more preferably 50 mol% to 70. More preferably, it is contained in mol%.

In addition, from the viewpoint of alkali developability, monomers having acidic groups, particularly carboxyl groups such as (meth) acrylic acid and itaconic acid, monomers having phenolic hydroxyl groups such as N-hydroxyphenylmaleimide, maleic anhydride and itaconic anhydride It is preferable to include a monomer having a carboxylic acid anhydride group such as a copolymerization component.
Among these, it is preferable to contain (meth) acrylic acid as a copolymerization component. The content of the acidic group is preferably 5 mol% or more, preferably 10 mol% to 30 mol%, when the total repeating unit contained in the specific resin of the present invention is 100 mol%. preferable.

In addition, from the viewpoint of ease of handling such as solubility in an organic solvent, it is preferable to include aryl (meth) acrylate, alkyl (meth) acrylate, and polyethyleneoxy (meth) acrylate that impart oil solubility as a copolymerization component.
Of these, aryl (meth) acrylate or alkyl (meth) acrylate is preferably included as a copolymerization component.

Examples of the aryl (meth) acrylate include benzyl methacrylate.
Examples of the alkyl (meth) acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 3-hydroxypropyl. Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as methacrylate, 4-hydroxybutyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, acrylic acid Hexyl, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, 3, -Alkyl acrylates such as epoxy cyclohexyl methyl acrylate, vinyl acrylate, 2-phenyl vinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacryl Acid butyl, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate , 2-phenyl vinyl methacrylate, 1-propenyl methacrylate, allyl meta Relate, 2-allyloxyethyl methacrylate, propargyl methacrylate, and the like.

Further, it is specified that a compound having a radical polymerizable double bond is further added to an unsaturated compound having a partial structure represented by the formula (I) and a resin containing a copolymerization component other than the compound. Since the resin can have a radiation-sensitive group, this is a more preferable embodiment.
The treatment method for adding a compound having a radical polymerizable double bond differs depending on the type of monomer to which the compound having a radical polymerizable double bond can be added. For example, carboxyl such as (meth) acrylic acid or itaconic acid When a monomer having a group is used, an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether and a radical A compound having a polymerizable double bond may be added. When a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride is used, 2-hydroxyethyl (meth) acrylate is used. Add compounds with hydroxyl groups and radical polymerizable double bonds such as Well, when a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzylglycidyl ether is used, A compound having an acid group such as (meth) acrylic acid and a radical polymerizable double bond may be added.

  Moreover, when making a specific resin contain a radiation sensitive group, as for content of the copolymerization component which has a radiation sensitive group, 20-40 mol% is preferable by the composition ratio in specific resin. By setting it within this range, the curability of the radiation-sensitive composition is increased, so that the linearity can be further improved and the residue can be reduced.

  The most preferable combination as a copolymerization component in the specific resin includes an unsaturated compound having a partial structure represented by the formula (I), methacrylic acid, acetoacetoxyethyl (meth) acrylate, and a partial structure represented by the formula (I). It is a copolymer of an unsaturated compound having methacrylic acid.

  Content of the partial structure represented by Formula (I) in specific resin is 1-20 mol%, 3-15 mol% is preferable, More preferably, it is 7-12 mol%. By setting it as this range, the improvement of linearity and the reduction effect of a residue can be heightened.

  As content of the copolymerization component containing the acidic group in specific resin, it is preferable that the acid value of specific resin is 50 mgKOH / g-200 mgKOH / g. By setting it as this range, the alkali developability of the colored radiation-sensitive composition is improved, and the pattern formability is particularly good.

  Moreover, specific resin made the partial structure represented by Formula (I) to the side chain of an acrylic resin by making the reactive compound which has the partial structure represented by Formula (I) react with an acrylic resin. Acrylic resin may be used.

The molecular weight of the specific resin is preferably 5000 to 30000 in terms of weight average molecular weight, more preferably 8000 to 25000, and most preferably 9000 to 20000. By setting it as this range, the solubility to a solvent and developability become favorable.
Here, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene. GPC was measured using HLC-8020GPC (manufactured by Tosoh Corporation), and the columns were measured as TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ200 (manufactured by Tosoh Corporation).

  The specific resin can be synthesized according to the method described in JP 2010-053307 A.

The colored radiation-sensitive composition of the present invention may contain one kind of specific resin, but may contain two or more kinds.
Further, the specific resin may be included in the colored radiation-sensitive composition and may be added in any step of the preparation of the colored radiation-sensitive composition, but is preferably added in the preparation of the colored radiation-sensitive composition.
The content of the specific resin in the colored radiation-sensitive composition of the present invention is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, based on the total solid content of the colored radiation-sensitive composition. 6% by mass is particularly preferred. By making it within this range, the effect of the present invention is sufficiently exhibited.

  In order to improve the S / N ratio of the solid-state imaging device, the coloring pattern is made thin, but the content of the colorant in the solid content of the colored radiation-sensitive composition is increased to realize the thin layer. In addition, the ratio of components such as resins and polymerizable compounds other than the colorant in the solid content decreases. However, by using (B) a specific resin, the difference in alkali dissolution rate (discrimination) between the exposed and unexposed areas becomes larger than before, the unexposed areas exhibit high developability, and the linearity of the pattern Improved and reduced residue. Therefore, even when the colorant content is high, the colored pattern in the exposed area is rectangular, reducing the residue around the pixel, and suppressing the surface roughness of the colored pattern and the exposure dose dependency (thickening of the line width). It becomes. This makes it possible to reduce the color pattern.

<(C) Polymerizable compound>
The radiation sensitive composition of the present invention contains (C) a polymerizable compound.
(C) Specifically, the polymerizable compound is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Among them, a polyfunctional polymerizable compound having 4 or more functional groups is preferable and 5 or more functional groups are more preferable.
Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.

More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. is there. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can also be suitably used in the present invention.

The polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples 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, trimethylolethanetri (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) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates and the like, which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
In addition, as other preferable polymerizable compounds, there are fluorene rings described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, etc., and an ethylenically unsaturated group is difunctional. The above-mentioned compounds and cardo resins can also be used.

  Moreover, as a compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group, paragraph numbers [0254] to [0257] of JP-A-2008-292970 are disclosed. Also suitable are the compounds described in.

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the said general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
In each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5), at least one of a plurality of Rs is —OC (═O) CH═CH ₂ or —OC. (= O) represents a group represented by C (CH ₃ ) ═CH ₂ .
Specific examples of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5) include the compounds described in paragraphs 0248 to 0251 of JP-A-2007-26979. It can be suitably used in the invention.

  Moreover, the compound which (meth) acrylate-ized after adding ethylene oxide and propylene oxide to the said polyfunctional alcohol described with the specific example as general formula (1) and (2) in Unexamined-Japanese-Patent No. 10-62986 is also, It can be used as a polymerizable compound.

  Among these, as the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available product: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product: KAYARAD DPHA; Nippon Kayaku Co., Ltd.) Manufactured by Nippon Kayaku Co., Ltd., and A-DPH-12E manufactured by Nippon Kayaku Co., Ltd., and a structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues. These oligomer types can also be used. Preferred embodiments of the polymerizable compound are shown below.

  As a polymeric compound, it is a polyfunctional monomer, Comprising: You may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. If the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. Non-aromatic carboxylic acid anhydrides may be reacted to introduce acid groups. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferred, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

In the colored radiation-sensitive composition of the present invention, one of these polymerizable compounds may be used alone, but it is difficult to obtain a single compound for the production of the polymerizable compound. You may mix and use the above.
Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as a polymeric compound as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

Moreover, it is also a preferable aspect to contain the polyfunctional monomer which has a caprolactone structure as a polymeric compound.
The polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, diester. Ε-caprolactone modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohol such as pentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone Can be mentioned. Especially, the polyfunctional monomer which has a caprolactone structure represented with the following general formula (Z-1) is preferable.

  In the general formula (Z-1), all six Rs are groups represented by the following general formula (Z-2), or 1 to 5 of the six Rs are represented by the following general formula (Z -2), and the remainder is a group represented by the following general formula (Z-3).

In General Formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.

In General Formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond. )

Such a polyfunctional monomer having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (1) to (3)). , Number of groups represented by formula (2) = 2, compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (2) = 3 , Compounds in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (2) = 6, compounds in which R ¹ are all hydrogen atoms), DPCA- 120 (a compound in which m = 2 in the same formula, the number of groups represented by formula (2) = 6, and all R ¹ are hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

The polymerizable compound in the present invention is preferably a polymerizable compound containing an alkyleneoxy group having 2 or more carbon atoms (such as an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group).
Among the polymerizable compounds containing an alkyleneoxy group having 2 or more carbon atoms, at least one selected from the group of compounds represented by the following general formula (i) or (ii) is particularly preferable.

In the general formula (i) and (ii), E are each _{independently, - ((CH 2) y} CH 2 O) -, or _{- ((CH 2) y CH} (CH 3) O) - represents, Each y independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In general formula (i), the sum total of the acryloyl group and methacryloyl group represented by X is 3 or 4, m represents the integer of 0-10 each independently, and the sum of each m is 0-40. It is an integer. However, when the total of each m is 0, any one of X is a carboxyl group.
In general formula (ii), the sum total of the acryloyl group and methacryloyl group represented by X is 5 or 6, each n independently represents an integer of 0 to 10, and the sum of each n is 0 to 60. It is an integer. However, when the total of each n is 0, any one of X is a carboxyl group.

In general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In general formula (i) or formula (ii) in the _{- ((CH 2) y CH} 2 O) - or _{- ((CH 2) y CH} (CH 3) O) - , the oxygen atom side ends Is preferred in which X is bonded to X.

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

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

Among the compounds represented by the general formulas (i) and (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
In particular, a polymerizable compound having an ethyleneoxy group and 5 or more (meth) acryloyl groups in the molecule is preferable. The total number of ethyleneoxy groups contained in the molecule is preferably 2 to 10, more preferably 4 to 8.
By incorporating a polymerizable compound having an ethyleneoxy group and five or more (meth) acryloyl groups in the molecule into the colored radiation-sensitive composition, the solubility of the unexposed area in an alkaline developer is improved, and exposure is performed. Since the discrimination between the portion and the non-exposed portion is facilitated, the linearity of the colored pattern is improved, and the residue on the colored pattern of the substrate and other colors can be reduced.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), among which exemplary compounds (a) to ( d) is preferable, and the effect of the present invention can be remarkably improved.

  Examples of commercially available polymerizable compounds represented by general formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Moreover, you may further mix | blend the polymeric compound of the other structure which has 2 or more polymeric groups with the colored radiation sensitive composition of this invention with a polymeric compound.
Examples of the “polymerizable compound having another structure having two or more polymerizable functional groups” include, for example, polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, and neopentyl glycol di (meth) acrylate. , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) ) A polyfunctional alcohol such as isocyanurate, glycerin or trimethylol ethane, which is added with ethylene oxide or propylene oxide and then (meth) acrylated. No. 708, JP-B-50-6034, JP-A-51-37193, etc., urethane acrylates, JP-A-48-64183, JP-B-49-43191, JP-B-52 Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid described in each publication such as -30490 can be mentioned.
Furthermore, Japan Adhesion Association Vol. 20, No. 7 (pages 300 to 308), which are introduced as photocurable monomers and oligomers, can also be used.

  As content of the polymeric compound in the coloring radiation sensitive composition of this invention, 2-50 mass% is preferable with respect to the total solid of this composition, 2-30 mass% is more preferable, Furthermore, 2-25 mass% is more preferable.

<(D) UV absorber>
The colored radiation-sensitive composition of the present invention contains an ultraviolet absorber.
[Ultraviolet absorber]
The curable composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, a compound represented by the following general formula (II) which is a conjugated diene compound is particularly preferable.

In the general formula (II), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² And do not represent hydrogen atoms at the same time. R ³ and R ⁴ each independently represents a monovalent group.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-hexyl group, a cyclohexyl group, and n-decyl. Group, n-dodecyl group, n-octadecyl group, eicosyl group, methoxyethyl group, ethoxypropyl group, 2-ethylhexyl group, hydroxyethyl group, chloropropyl group, N, N-diethylaminopropyl group, cyanoethyl group, phenethyl group Group, benzyl group, pt-butylphenethyl group, pt-octylphenoxyethyl group, 3- (2,4-di-t-amylphenoxy) propyl group, ethoxycarbonylmethyl group, 2- (2-hydroxyethoxy) ) Ethyl group, 2-furylethyl group and the like, and methyl group, ethyl group, propyl group, n-butyl group and n-hexyl group are preferred. Arbitrariness.
The alkyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent of the alkyl group having a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, Halogen atom, acylamino group, acyl group, alkylthio group, arylthio group, hydroxy group, cyano group, alkyloxycarbonyl group, aryloxycarbonyl group, substituted carbamoyl group, substituted sulfamoyl group, nitro group, substituted amino group, alkylsulfonyl group, An arylsulfonyl group etc. are mentioned.

The aryl group having 6 to 20 carbon atoms represented by R ¹ and R ² may be a single ring or a condensed ring, and is any of a substituted aryl group having a substituent or an unsubstituted aryl group. There may be. For example, a phenyl group, 1-naphthyl group, 2-naphthyl group, anthryl group, phenanthryl group, indenyl group, acenabutenyl group, fluorenyl group, etc. can be mentioned. Examples of the substituent of the substituted aryl group having a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a halogen atom, an acylamino group, an acyl group, an alkylthio group, an arylthio group, a hydroxy group, and a cyano group. Group, alkyloxycarbonyl group, aryloxycarbonyl group, substituted carbamoyl group, substituted sulfamoyl group, nitro group, substituted amino group, alkylsulfonyl group, arylsulfonyl group and the like. Of these, a substituted or unsubstituted phenyl group, 1-naphthyl group, and 2-naphthyl group are preferable.

R ¹ and R ² may form a cyclic amino group together with the nitrogen atom to which R ¹ and R ² are bonded. Examples of the cyclic amino group include piperidino group, morpholino group, pyrrolidino group, hexahydroazepino group, piperazino group and the like.

Among the above, R ¹ and R ² are each a lower alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, octyl). , 2-ethylhexyl, tert-octyl, etc.) or a substituted or unsubstituted phenyl group (eg, tolyl group, phenyl group, anisyl group, mesityl group, chlorophenyl group, 2,4-di-tert-amylphenyl group, etc.) Is preferred. It is also preferred that R ¹ and R ² are combined to form a ring (for example, a piperidine ring, a pyrrolidine ring, a morpholine ring) containing the nitrogen atom represented by N in the formula.

In the general formula (II), the monovalent group represented by R ³ and R ⁴ represents an electron withdrawing group. Here, the electron withdrawing group is an electron withdrawing group having a Hammett's substituent constant σ _p value (hereinafter simply referred to as “σ _p value”) of 0.20 or more and 1.0 or less. Preferably, it is an electron withdrawing group having a σ _p value of 0.30 or more and 0.8 or less.
Hammett's rule was found in 1935 by L. L. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include σ _p value and σ _m value, and these values are described in many general books. A. Dean ed. “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemical Domains Extra”, 122, 96-103, 1979 (Nan-Edo), Chemical Reviews, 91, 165-195, detailed in 1991. In the present invention, it does not mean that the values known in the literature described in these documents are limited to only certain substituents, but within the range when measured based on Hammett's law even if the value is unknown. Of course, it is included as long as it is included.

Specific examples of the electron withdrawing group having a σ _p value of 0.20 or more and 1.0 or less include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, and a nitro group. Dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, An alkyl group substituted with at least two or more halogen atoms, an alkoxy group substituted with at least two or more halogen atoms, an aryloxy group substituted with at least two or more halogen atoms, or at least two or more halogen atoms Alkyl substituted with Amino group, at least two an alkylthio group substituted with a halogen atom, sigma _p value of 0.20 or more other electron-withdrawing aryl group substituted by group, a heterocyclic group, a chlorine atom, a bromine atom, an azo Group, or selenocyanate group. Of these substituents, the group that can further have a substituent may further have a substituent as described above.

Among these, as R ³ and R ⁴ , an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, and a sulfamoyl group are preferable. In particular, an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, and a sulfamoyl group are preferable.
Among the above, in the present invention, R ³ is preferably a group selected from a cyano group, —COOR ⁵ , —CONHR ⁵ , —COR ⁵ , —SO ₂ R ⁵ , and R ⁴ is a cyano group. A group selected from the group, —COOR ⁶ , —CONHR ⁶ , —COR ⁶ , —SO ₂ R ⁶ is preferred. R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by R ⁵ and R ^{6 have the same} meanings as those in R ¹ and R ² , and the preferred embodiments are also the same.
R ³ and R ⁴ may be bonded to each other to form a ring.

Moreover, at least one of the above R ¹ , R ² , R ³ , and R ⁴ may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It may be a copolymer with another monomer. In the case of the copolymer, other monomers include acrylic acid, α-chloroacrylic acid, α-alacrylic acid (for example, esters derived from acrylic acids such as methacrylic acid, preferably lower alkyl esters and amides such as Acrylamide, methacrylamide, t-butyl acrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, octyl methacrylate , Lauryl methacrylate, methylenebisacrylamide, etc.), vinyl esters (eg, vinyl acetate, vinyl propionate, vinyl laurate, etc.), acrylonitrile, methacryloni Tolyl, aromatic vinyl compounds (for example, styrene and its derivatives such as vinyl toluene, divinylbenzene, vinyl acetophenone, sulfostyrene, and styrene sulfinic acid), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether ( For example, vinyl ethyl ether), maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- and 4-vinylpyridine, and the like.
Of these, acrylic acid esters, methacrylic acid esters, and aromatic vinyl compounds are particularly preferable.
Two or more of the other monomer compounds can be used together. For example, n-butyl acrylate and divinylbenzene, styrene and methyl methacrylate, methyl acrylate and methacrylate acid, or the like can be used in combination.

  Hereinafter, preferable specific examples [Exemplary compounds (1) to (14)] of the compound represented by the general formula (II) are shown. However, the present invention is not limited to these.

  The ultraviolet absorbers represented by the general formula (II) are described in JP-B No. 44-29620, JP-A No. 53-128333, JP-A No. 61-169831, JP-A No. 63-53543, and JP-A No. 63-53544. In addition, it can be synthesized by the methods described in JP-A 63-56651 and other publications and WO 2009/123109 pamphlet. Specifically, the exemplified compound (1) can be synthesized by the method described in paragraph No. 0040 of WO2009 / 123109 pamphlet.

In addition, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based ultraviolet absorbers, and the like can be used as the ultraviolet absorber.
Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and the like. Examples of benzophenone-based UV absorbers include 2,2′-dihydroxy-4- Methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- And hydroxy-4-octoxybenzophenone. Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3). '-Tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- ( 2'-hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzoto Azole, 2- [2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole and the like.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, and the like. Furthermore, as an example of a triazine ultraviolet absorber, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) ) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as 1,3,5-triazine and 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy); 3-methyl-4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6 Bis (hydroxyphenyl) triazine compounds such as-(2,4-dimethylphenyl) -1,3,5-triazine; 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4- Dibutoxyphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris [2- And tris (hydroxyphenyl) triazine compounds such as hydroxy-4- (3-butoxy-2-hydroxypropyloxy) phenyl] -1,3,5-triazine.
In the present invention, the various ultraviolet absorbers may be used alone or in combination of two or more.

  Preferred ultraviolet absorbers are exemplified compounds (1) to (14), and particularly preferred compounds are exemplified compounds (2) and (11).

The colored radiation-sensitive composition of the present invention is characterized by containing 0.1% by mass to 10% by mass of an ultraviolet absorber with respect to the solid content of the colored radiation-sensitive composition.
Furthermore, as content of a preferable ultraviolet absorber, it is 0.5 mass%-6 mass% with respect to solid content of a coloring radiation sensitive composition, and 1 mass%-5 mass% are more preferable.
By setting it as this range, when a colored pattern is formed using the colored radiation-sensitive composition of the present invention, the linearity of the colored pattern is improved, and the residue on the colored pattern of the substrate and other colors is improved. Can be reduced.

<(E) Photopolymerization initiator>
The colored radiation-sensitive composition of the present invention preferably contains (E) a photopolymerization initiator.
As the (E) photopolymerization initiator (hereinafter sometimes simply referred to as “polymerization initiator”) in the present invention, those known as photopolymerization initiators described below can be used.

The photopolymerization initiator in the present invention is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

  Examples of the (E) photopolymerization initiator in the present invention include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexa Examples thereof include oxime compounds such as arylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones. Among these, oxime compounds are preferable.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), a compound described in JP-A-62-258241, a compound described in JP-A-5-281728, a compound described in JP-A-5-34920, and U.S. Pat. No. 4,221,976. And compounds described in the specification.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4 Oxadiazole, etc.).

  In addition, as polymerization initiators other than those described above, polyhalogen compounds (for example, four-phenyl acridine, such as 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane), N-phenylglycine, and the like. Carbon bromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (for example, 3- (2-benzofuranoyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1- Pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis ( 5,7-di-n-propoxycoumarin), 3,3′-carbo Rubis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, etc.), acylphosphine oxides (for example, bis (2,4 , 6-Trimethylbenzoyl) -phenylphosphite Oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl)- Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.) Examples thereof include compounds described in JP-A Nos. 53-133428, 57-1819, 57-6096, and US Pat. No. 3,615,455.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bisdicyclohexyl) Amino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzene Zophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzo Down propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

As the polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source of 365 nm or 405 nm can also be used. As the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

  More preferred examples of the polymerization initiator include oxime compounds. Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.

  Examples of oxime compounds such as oxime derivatives that are preferably used as a polymerization initiator in the present invention include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyimibutane. 2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4- Toluenesulfonyloxy) iminobutan-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

Examples of oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 15
6-162, Journal of Photopolymer Science and Technology (1995), pp. 6-162. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE OX-01 (manufactured by BASF) and IRGACURE OXE-02 (manufactured by BASF) are also preferably used as commercial products.

  Further, as oxime compounds other than the above, compounds described in JP-T 2009-519904, in which oxime is linked to the N-position of carbazole, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, and dyes Compounds described in JP2010-15025A and US Patent Publication No. 2009-292209, in which a nitro group is introduced at the site, ketoxime compounds described in International Patent Publication No. 2009-131189, triazine skeleton and oxime skeleton are the same molecule A compound described in U.S. Pat. No. 7,556,910 and a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source may be used.

Preferably, it can also be suitably used for the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744. Among the cyclic oxime compounds, the cyclic oxime compounds fused to the carbazole dyes described in JP2010-32985A and JP2010-185072A in particular have high light absorptivity from the viewpoint of high sensitivity. preferable.
In addition, the compound described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can be preferably used because it can achieve high sensitivity by regenerating the active radical from the polymerization inert radical. it can.

Most preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-267979 and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

In General Formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In General Formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

  The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, or a decyl group. , Dodecyl group, octadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2- Methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and , 3 Nitorofenashiru group can be exemplified.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, specifically, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-anthryl group. 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-tolyl group, m-tolyl group, p -Tolyl group, xylyl group, o-cumenyl group, m-cumenyl group and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, full Oranthenyl, acenaphthylenyl, aceanthrylenyl, phenalenyl, fluorenyl, ant Ryl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrycenyl group, naphthacenyl group, pleiadenyl group, picenyl group, perylenyl group, pentaphenyl group, Examples thereof include a pentacenyl group, a tetraphenylenyl group, a hexaphenyl group, a hexacenyl group, a ruvicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an oberenyl group.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2 -Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, and And 4-methoxybenzoyl group.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a hexyloxy group. Examples thereof include a carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanyl. Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl , 4-fluorophenyl oxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.

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

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

  Specific examples of the arylthiocarbonyl group which may have a substituent include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, and a 4-phenylsulfanylphenylthiocarbonyl group. 4-dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3 -Chlorophenylthiocarbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenyl Two thiocarbonyl group, and a and a 4-methoxyphenylthiocarbonyl group.

  In the general formula (OX-1), the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Of these, the structures shown below are particularly preferred.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in General Formula (OX-2) described later, and preferred examples are also the same.

In general formula (OX-1), examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A in the formula (OX-1) is an unsubstituted alkylene group, an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, dodecyl) from the viewpoint of increasing sensitivity and suppressing coloring due to heating. Group) substituted alkylene group, alkenyl group (eg vinyl group, allyl group) alkylene group, aryl group (eg phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl) Group, a phenanthryl group, and a styryl group) are preferable.

In general formula (OX-1), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent. Examples of the substituent include the same substituents as those introduced into the substituted aryl group mentioned above as specific examples of the aryl group which may have a substituent.
Among these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the general formula (OX-1), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar in the general formula (OX-1) and S adjacent thereto is a structure shown below. . Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is preferably a compound represented by the following general formula (OX-2).

(In Formula (OX-2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0 to 0. (It is an integer of 5.)
R, A and Ar in the formula (OX-2) have the same meanings as R, A and Ar in the formula (OX-1), and preferred examples are also the same.

  In the general formula (OX-2), the monovalent substituent represented by X includes an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, and a heterocyclic ring. Group and halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among these, as X in the general formula (OX-2), an alkyl group is preferable from the viewpoints of solvent solubility and improvement of absorption efficiency in a long wavelength region.
Moreover, n in a formula (OX-2) represents the integer of 0-5, and the integer of 0-2 is preferable.

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

  As the photopolymerization initiator, those having the structure shown below are preferable from the viewpoint of increasing sensitivity.

  Furthermore, the oxime compound is preferably a compound represented by the following general formula (OX-3).

In general formula (OX-3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5. . )
R, X, A, Ar, and n in General Formula (OX-3) have the same meanings as R, X, A, Ar, and n in General Formula (OX-2), respectively, and preferred examples thereof are also the same. It is.

  Specific examples of oxime compounds that can be suitably used are shown below, but the present invention is not limited thereto.

  The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 455 nm.

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

The polymerization initiator used in the present invention may be used in combination of two or more as required.

  The photopolymerization initiator (E) used in the colored radiation-sensitive composition of the present invention includes a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acyl from the viewpoint of exposure sensitivity. Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyl oxadi Compounds selected from the group consisting of azole compounds and 3-aryl substituted coumarin compounds are preferred.

  More preferred are trihalomethyltriazine compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone compound, trihalomethyltriazine compound, α-aminoketone Most preferred is at least one compound selected from the group consisting of compounds, oxime compounds, triallylimidazole dimer, and benzophenone compounds.

  In particular, when the colored radiation-sensitive composition of the present invention is used for producing a color filter provided in a solid-state imaging device, in order to form a fine pattern with a sharp shape and improve the linearity of the colored pattern, It is important that the development is performed with no residue in the non-exposed area as well as the curability. From such a viewpoint, it is particularly preferable to use an oxime compound as the polymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and it is necessary to keep the addition amount of a polymerization initiator low. Considering these points, it is most preferable to use an oxime compound as the polymerization initiator (E) for forming a fine pattern such as a solid-state imaging device.

  The content of the (E) polymerization initiator contained in the colored radiation-sensitive composition of the present invention is 0.1% by mass or more and 50% by mass or less based on the total solid content of the colored radiation-sensitive composition. More preferably, it is 0.5 mass% or more and 20 mass% or less, More preferably, it is 1 mass% or more and 15 mass% or less. Within this range, good sensitivity and pattern formability can be obtained.

<(F) Organic solvent>
The colored radiation-sensitive composition of the present invention contains an organic solvent.
Examples of the organic solvent include the following.
Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate ( For example, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxypropionates (eg, Methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate)), 2- Oxypro Onion acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate) Propyl acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, 2-methoxy-2-methyl Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. As ethers, for example, Ethylene 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., and ketones, for example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc., and aromatic hydrocarbons, for example, toluene, xylene, etc. Are preferable.

An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
When two or more organic solvents are used in combination, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid are particularly preferable. It is a mixed solution composed of two or more selected from methyl, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

  The amount of the organic solvent contained in the colored radiation-sensitive composition is preferably 10% by mass to 90% by mass, and 20% by mass to 80% by mass with respect to the total amount of the colored radiation-sensitive composition. Is more preferable, and it is still more preferable that it is 25 mass%-75 mass%.

<Sensitizer>
The colored radiation-sensitive composition of the present invention may contain a sensitizer for the purpose of improving the generation efficiency of the photopolymerization initiator and increasing the photosensitive wavelength. Examples of the sensitizer include a sensitizer having an absorption wavelength in a wavelength region of 300 nm to 450 nm.

  Examples of the sensitizer include polynuclear aromatics such as phenanthrene, anthracene, pyrene, perylene, triphenylene, and 9,10-dialkoxyanthracene, xanthene such as fluorescein, eosin, erythrosine, rhodamine B, and rose bengal. Thioxanthones, cyanines, merocyanines, phthalocyanines, thiazines such as thionine, methylene blue, toluidine blue, acridines, anthraquinones, squaliums, coumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds , Diphenylmethane, triphenylmethane, distyrylbenzenes, carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazo Triazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, aromatic ketone compounds such as Michler's ketone, and heterocyclic compounds such as N- aryl oxazolidinone and the like.

<Chain transfer agent>
Depending on the photopolymerization initiator used, it is preferable to add a chain transfer agent to the colored radiation-sensitive composition of the present invention. Examples of chain transfer agents include N, N-dialkylaminobenzoic acid alkyl esters and thiol compounds. Examples of thiol compounds include 2-mercaptobenzothiazole, 2-mercapto-1-phenylbenzimidazole, and 3-mercaptopropion. An acid etc. can be used individually or in mixture of 2 or more types.

<Alkali-soluble resin>
The colored radiation-sensitive composition of the present invention preferably also contains (B) an alkali-soluble resin having a structure different from that of the specific resin. By containing the alkali-soluble resin, the developability and pattern formability are further improved.
When the specific resin has an acid group and exhibits alkali solubility, the specific resin is also an alkali-soluble resin. Here, an alkali-soluble resin having a structure different from that of the specific resin will be described below.
The alkali-soluble resin may be a linear organic polymer having a structure different from that of the specific resin, and in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). Can be appropriately selected from alkali-soluble resins having at least one group that promotes alkali solubility.
As the alkali-soluble resin in the present invention, it is preferable to use at least one of a specific resin that exhibits alkali-solubility and a linear organic polymer having a structure different from that of the specific resin. Good.

As a linear organic polymer having a structure different from that of the specific resin, from the viewpoint of heat resistance, polyhydroxystyrene resin, polysiloxane resin, acrylic resin, acrylamide resin, acrylic / acrylamide copolymer resin From the viewpoint of developing property control, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. The group is soluble in an organic solvent and developed with a weak alkaline aqueous solution. Possible are preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.
Examples of the monomer capable of imparting an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types. In order to introduce an acid group into an alkali-soluble binder, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component. In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.

  For the production of an alkali-soluble resin, which is a linear organic polymer having a structure different from that of the specific resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  The alkali-soluble resin, which is a linear organic polymer having a structure different from that of the specific resin, is preferably a polymer having a carboxylic acid in the side chain, such as a methacrylic acid copolymer, an acrylic acid copolymer, and an itaconic acid copolymer. , Crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, alkali-soluble phenol resin such as novolac resin, etc., acidic cellulose derivative having carboxylic acid in the side chain, polymer having hydroxyl group The thing which added the acid anhydride is mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macro Examples of N-substituted maleimide monomers described in JP-A-10-300922 such as monomers and polymethylmethacrylate macromonomers include N-phenylmaleimide and N-cyclohexylmaleimide. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

As alkali-soluble phenol resin, when the colored photosensitive composition of this invention makes a positive composition, it can use suitably. Examples of the alkali-soluble phenol resin include novolak resins and vinyl polymers.
Examples of the novolac resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A.
Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, and benzaldehyde.
The said phenols and aldehydes can be used individually or in combination of 2 or more types.

  Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol or a mixture thereof and formalin.

  The novolak resin may be adjusted in molecular weight distribution by means of fractionation or the like. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with the said novolak resin.

Moreover, in order to improve the crosslinking efficiency of the colored radiation-sensitive composition in the present invention, an alkali-soluble resin having a polymerizable group may be used. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the above-mentioned polymer containing a polymerizable group include: Dynal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Manufactured by Diamond Shamrock Co. Ltd.), Biscote R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industry Co., Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like.
As an alkali-soluble resin containing these polymerizable groups, an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group; Urethane-modified polymerizable double bond-containing acrylic resin obtained by the above reaction, unsaturated group-containing acrylic obtained by reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule Resin, acid pendant type epoxy acrylate resin, OH group-containing acrylic resin and polymerizable double bond-containing acrylic resin obtained by reacting a polymerizable double bond, OH group-containing acrylic resin and isocyanate Resin obtained by reacting a compound having a polymerizable group, Japanese Patent Application Laid-Open No. 2002-229207 And a resin obtained by performing a basic treatment on a resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2003-335814 Etc. are preferable.

  As the alkali-soluble resin, in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are suitable. In addition, a copolymer of 2-hydroxyethyl methacrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2-hydroxy -3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / Benzyl methacrylate / methacrylic acid copolymer.

The acid value of the alkali-soluble resin which is a linear organic polymer having a structure different from that of the specific resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, Most preferably, it is 70-120 mgKOH / g.
In addition, the weight average molecular weight (Mw) of the alkali-soluble resin, which is a linear organic polymer having a structure different from that of the specific resin, is preferably 2,000 to 50,000, and more preferably 5,000 to 30,000. Preferably, 7,000 to 20,000 is most preferable.

  The content of the alkali-soluble resin, which is a linear organic polymer having a structure different from that of the specific resin, in the colored radiation-sensitive composition is 1 to 15% by mass with respect to the total solid content of the composition. More preferably, it is 2-12 mass%, Most preferably, it is 3-10 mass%. However, it is preferable that it is 40 mass% or less with respect to content of the specific resin in this invention.

<Polymerization inhibitor>
In the colored radiation-sensitive composition of the present invention, a small amount of a polymerization inhibitor should be added in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored radiation-sensitive composition. Is desirable.
Examples of the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like. Of these, p-methoxyphenol is preferred.
The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the colored radiation-sensitive composition.

<Board adhesive>
Furthermore, in this invention, you may add the board | substrate adhesive agent which can improve board | substrate adhesiveness to a coloring radiation sensitive composition.
As the substrate adhesion agent, it is preferable to use a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent. Examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, and γ-mercaptopropyl. Examples include trimethoxysilane, γ-aminopropyltriethoxysilane, and phenyltrimethoxysilane. Among these, γ-methacryloxypropyltrimethoxysilane is preferable as the substrate adhesion agent.

  The content of the substrate adhesive is based on the total solid content of the radiation-sensitive composition of the present invention from the viewpoint of leaving no residue in the unexposed area when the colored radiation-sensitive composition is exposed and developed. It is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less, and particularly preferably 1% by mass or more and 10% by mass or less.

<Surfactant>
Various surfactants may be added to the colored radiation-sensitive composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used.

In particular, since the colored radiation-sensitive composition of the present invention contains a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the coating thickness is uniform. And liquid-saving properties can be further improved.
That is, in the case of forming a film using a coating liquid to which a colored radiation-sensitive composition containing a fluorosurfactant is applied, the surface to be coated is reduced by reducing the interfacial tension between the surface to be coated and the coating liquid. The wettability is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a colored radiation-sensitive composition. .

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (above, manufactured by Asahi Glass Co., Ltd.).

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sol Perth 20000 (manufactured by Nippon Lubrizol Corporation), Pionin D-6112-W (produced by Takemoto Oil & Fat Co., Ltd.), and the like.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

  Examples of the silicone-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.

Only one type of surfactant may be used, or two or more types may be combined.
The addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the colored radiation-sensitive composition. is there.

<Other ingredients>
In the colored radiation-sensitive composition of the present invention, a chain transfer agent such as N, N-dialkylaminobenzoic acid alkyl ester and 2-mercaptobenzothiazole, an azo compound, a peroxide compound, etc. Thermal polymerization initiators, thermal polymerization components, film strength, plasticizers such as epoxy compounds and dioctyl phthalate for the purpose of increasing the sensitivity and sensitivity, developability improvers such as low molecular weight organic carboxylic acids, other fillers, Various additives such as a polymer compound other than the specific binder and the alkali-soluble resin, an antioxidant, and an aggregation inhibitor can be contained.
Further, a thermosetting agent can be added to increase the degree of curing of the film by post-heating after development. Examples of the thermosetting agent include thermal polymerization initiators such as azo compounds and peroxides, novolac resins, resole resins, epoxy compounds, and styrene compounds.

-Preparation of colored radiation-sensitive composition-
The colored radiation-sensitive composition of the present invention is preferably prepared using an organic solvent together with the components (A) to (D) described above and other components used as desired.

  The colored radiation-sensitive composition of the present invention can be applied to color filters for liquid crystal display devices, printing inks, inkjet inks, etc., in addition to the production of color filters used in solid-state imaging devices.

  The colored radiation-sensitive composition of the present invention is excellent in pigment dispersion stability and developability even when containing a fine pigment at a high concentration, and can form a colored region with high definition and good color characteristics. Even when a color filter for a solid-state image sensor is manufactured, particularly when a film thickness of 0.8 μm or less, preferably 0.1 μm to 0.5 μm is formed, the effect is remarkable.

  Since the colored radiation-sensitive composition of the present invention is excellent in dispersion stability, it is applied to the formation of a color filter provided in a liquid crystal display device excellent in color reproducibility or a solid-state imaging device excellent in resolution. In this case, since it is advantageous in that a thin film can be formed, it is preferable to prepare a mode in which the pigment is contained at a high concentration in the application.

  As the pigment concentration in the colored radiation-sensitive composition of the present invention, the total solid content of the colored radiation-sensitive composition (that is, pigment, dispersant, specific resin, alkali-soluble resin, polymerizable compound, photopolymerizable initiator, And 40% by mass or more, more preferably 45% by mass or more, based on the total mass of the components excluding the solvent, such as other additives.

The colored radiation-sensitive composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. If it is conventionally used for the filtration use etc., it can use without being specifically limited. For example, fluorine resins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), etc. Filter. Among these materials, polypropylene (including high density polypropylene) is preferable.
The filter has a pore diameter of about 0.01 to 7.0 μm, preferably about 0.01 to 2.5 μm, and more preferably about 0.01 to 2.0 μm. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of the uniform and smooth coloring radiation sensitive composition in a post process.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more.
Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
As the second filter, a filter formed of the same material as the first filter described above can be used.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

[Color filter and manufacturing method thereof]
Next, the color filter of the present invention and the manufacturing method thereof will be described.
The color filter of the present invention has a colored region (colored pattern) formed using the colored radiation-sensitive composition of the present invention on a substrate.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

  The method for producing a color filter of the present invention includes a step of forming a radiation-sensitive composition layer (colored layer) by applying the radiation-sensitive composition of the present invention onto a substrate (colored layer forming step), and the radiation-sensitive composition. A step of exposing the photosensitive composition layer in a pattern (exposure step) and a step of developing the radiation-sensitive composition layer after exposure to form a colored pattern (development step).

<Colored layer forming step>
In the colored layer forming step, the colored radiation-sensitive composition of the present invention is applied onto the substrate body to form a colored layer (radiation-sensitive composition layer) comprising the colored radiation-sensitive composition.

Examples of the substrate that can be used in this step include a non-alkali glass, soda glass, and Pyrex (registered trademark) used in a CCD or CMOS photoelectric conversion element substrate, a silicon substrate, a liquid crystal display device, or the like used in a solid-state imaging device. Examples thereof include glass, quartz glass, and those obtained by attaching a transparent conductive film thereto. In some cases, a black matrix for isolating each pixel is formed on these substrates.
Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.

  As a coating method of the colored radiation-sensitive composition of the present invention on the substrate, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied. .

  The colored layer (colored radiation-sensitive composition layer) applied on the substrate can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, oven, or the like.

  The coating thickness of the colored layer after drying (hereinafter referred to as “dry thickness” as appropriate) is as follows. From the viewpoint of ensuring color density, light in an oblique direction does not reach the light receiving portion, and the edge and center of the device. From the viewpoint of reducing problems such as a significant difference in the light collection rate, 0.05 μm or more and less than 1.0 μm is preferable, 0.1 μm or more and 0.8 μm or less is more preferable, 0.2 μm or more and 0.7 μm The following are particularly preferred:

<Exposure process>
In the exposure step, the colored layer (radiation sensitive composition layer) formed in the colored layer forming step is exposed in a pattern.
In the exposure in this step, the colored layer is preferably exposed by exposing it through a predetermined mask pattern and curing only the coating film portion irradiated with light. As radiation that can be used for exposure, radiation such as g-line, h-line, and i-line is particularly preferably used. Irradiation dose is preferably ^{30mJ / cm 2 ~1500mJ / cm 2} , more preferably ^{50mJ / cm 2 ~1000mJ / cm 2} , 80mJ / cm 2 ~500mJ / cm 2 being most preferred.

<Development process>
Subsequent to the exposure step, an alkali development treatment (development step) is performed to elute the uncured portion after the exposure into the developer and leave the photocured portion. By this development step, a patterned film composed of pixels of each color (for example, 3 colors or 4 colors) can be formed.
The development method may be any of a dip method, a shower method, a spray method, a paddle method, etc., and a swing method, a spin method, an ultrasonic method, or the like may be combined therewith.
Before the developer is touched, the surface to be developed can be previously moistened with water or the like to prevent uneven development.

As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.
Examples of the alkaline agent contained in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, Organic alkali compounds such as 0] -7-undecene, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like.
As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water so that the concentration is 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass is preferably used. . In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans (rinse) with a pure water after image development.

Next, excess developer is washed away and dried.
In the production method of the present invention, after the above-described colored layer forming step, exposure step, and development step, the formed colored pattern is cured by post-heating (post-baking) or post-exposure, if necessary. A curing step may be included. The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 270 ° C. is performed. In the case of using light, it can be performed by g-line, h-line, i-line, excimer laser such as KrF or ArF, electron beam, X-ray, etc., but with an existing high-pressure mercury lamp at a low temperature of about 20-50 ° C. Preferably, the irradiation time is 10 seconds to 180 seconds, preferably 30 seconds to 60 seconds. In the case of combined use of post-exposure and post-heating, post-exposure is preferably performed first.

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

  Since the color filter of the present invention is produced using the colored radiation-sensitive composition of the present invention having excellent exposure sensitivity, the cured composition in the exposed area is excellent in adhesion to the substrate and development resistance. The adhesion between the formed colored pattern and the substrate is high, and the pattern giving a desired cross-sectional shape has fine colored pixels.

  The colored radiation-sensitive composition of the present invention can be easily cleaned and removed using a known cleaning liquid even when it adheres to, for example, a nozzle of a coating apparatus discharge section, a piping section of a coating apparatus, or the inside of a coating apparatus. . In this case, in order to perform more efficient cleaning and removal, it is preferable to use the organic solvent described above as the cleaning liquid as the organic solvent contained in the colored radiation-sensitive composition of the present invention.

JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP 2007-2101 A, JP 2007-2102 A, JP 2007-281523 A, etc. are also preferably used as cleaning liquids for cleaning and removing the colored radiation-sensitive composition of the present invention. Can do.
As the cleaning liquid, it is preferable to use alkylene glycol monoalkyl ether carboxylate or alkylene glycol monoalkyl ether.
These organic solvents that can be used as the cleaning liquid may be used alone or in combination of two or more.
When mixing 2 or more types of organic solvents, the mixed solvent formed by mixing the organic solvent which has a hydroxyl group, and the organic solvent which does not have a hydroxyl group is preferable. The mass ratio of the organic solvent having a hydroxyl group and the organic solvent not having a hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. The mixed solvent is a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), and the ratio is particularly preferably 60/40.
In addition, in order to improve the permeability of the cleaning liquid to the colored radiation-sensitive composition, the surfactant described above as a surfactant that may be contained in the colored radiation-sensitive composition may be added to the cleaning liquid.

  The color filter of the present invention produced by the method for producing a color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD and a CMOS, and also an image display device such as electronic paper and organic EL, a liquid crystal It can be suitably used for a display device or the like. In particular, it is suitable for a high-resolution CCD or CMOS solid-state imaging device exceeding 1 million pixels. The color filter of the present invention can also be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD element and a microlens for condensing light.

[Solid-state imaging device]
The solid-state imaging device of the present invention includes the color filter of the present invention. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter for the solid-state imaging device of the present invention, and is not particularly limited as long as the configuration functions as a solid-state imaging device. Can be mentioned.

A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on a substrate, and a photo is formed on the photodiode and the transfer electrode. A device having a light-shielding film made of tungsten or the like that is open only in the light-receiving portion of the diode, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion The color filter for a solid-state imaging device of the present invention is provided on the protective film.
Further, a configuration having light collecting means (for example, a microlens, etc., the same shall apply hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light collecting means on the color filter. Etc.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

[Production of silicon wafer with undercoat layer]
An undercoat layer composition is prepared according to the composition of the undercoat layer below, and a coating film is formed by applying the composition uniformly on a silicon wafer by spin coating, and the formed coating film is formed on a hot plate at 230 ° C. Heat treatment was performed for 120 seconds above. The spin coating speed was adjusted so that the thickness of the coating film after the heat treatment was about 0.1 μm.
Thus, a silicon wafer with an undercoat layer in which an undercoat layer was formed on the silicon wafer was obtained.

(Composition of composition for undercoat layer)
Organic solvent: Propylene glycol methyl ether acetate (hereinafter referred to as PGMEA) 54.56 parts Organic solvent: ethoxyethyl propionate (hereinafter referred to as EEP) 32.42 parts Binder: Product name, manufactured by Daicel Cyclomer P CR-1000 12.19 parts Fluorosurfactant: manufactured by DIC, trade name MegaFuck F-781, 0.83 part of 0.2% EEP solution

[Preparation of red pigment dispersion]
Using a zirconia bead having a diameter of 0.3 mm, a mixed solution having the following composition was mixed and dispersed for 3 hours in a bead mill (high pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.)). Thus, a pigment dispersion R-1 was prepared.
(composition)
-Red pigment: CIPigment Red254 (made by company) 4.74 parts-Yellow pigment: CIPigment Yellow139 (made by company) 2.11 parts-Dispersing resin: made by Nippon Shokubai Co., Ltd., trade name: Acrycure RD-F8 4.69 Parts / organic solvent: PGMEA 51.75 parts

[Preparation of green pigment dispersion]
Using a zirconia bead having a diameter of 0.3 mm, a mixed solution having the following composition was mixed and dispersed for 3 hours in a bead mill (high pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.)). Thus, a pigment dispersion G-1 was prepared.
(composition)
Green pigment: CIPigment Green36 (manufactured by company) 2.26 parts Yellow pigment: CIPigment Yellow150 (manufactured by company company) 2.19 parts Dispersing resin: manufactured by Fujikura Kasei Co., Ltd., trade name: Acrybase FFS-6824 (molecular weight 10,000) ) 3.09 parts ・ Organic solvent: PGMEA 28.99 parts ・ Organic solvent: cyclohexanone 2.36 parts

[Preparation of green colored radiation-sensitive composition]
A green colored radiation-sensitive composition was prepared with the following composition. This green colored radiation-sensitive composition is not the colored radiation-sensitive composition of the present invention.
(composition)
Organic solvent: PGMEA 47.06 partsResin: 5.94 parts of the following A-1 Polymerizable compound: A-DPH-12E (C-1) 2.05 parts manufactured by Nippon Kayaku Co., Ltd. Polymerization Compound: Nippon Kayaku Co., Ltd., Kayarad DPHA 0.69 parts (dipentaerythritol hexaacrylate)
-Photopolymerization initiator: BASF, Irgacure OXE-02 (E-1 below) 0.34 parts-Pigment dispersion G-1 38.89 parts-Fluorosurfactant: DIC, trade name Megafac F-781, 0.2% PGMEA solution 4.17 parts Nonionic surfactant: Takemoto Yushi Co., Ltd., Pionein D-6112-W 0.18 parts UV absorber: D-1 0.72 below Part / polymerization inhibitor: p-methoxyphenol 0.001 part

[Preparation of a substrate having a green coloring pattern]
On the undercoat layer of the silicon wafer substrate with the undercoat layer, the green colored radiation-sensitive composition obtained above is applied so that the thickness of the colored layer after drying is 0.4 μm. A colored layer was formed. And it heat-processed for 120 second (prebaking) using the 100 degreeC hotplate. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), the light having a wavelength of 365 nm is passed through a Bayer pattern mask having a pattern of 1.4 μm square, and the colored layer is exposed to 300 mJ / cm ² . 200 repeated patterns were irradiated on the entire surface of the wafer. Thereafter, the silicon wafer substrate on which the colored layer is formed is placed on a horizontal rotating table of a spin shower developing machine (DW-30 type; manufactured by Chemitronics), and an alkali developer CD-2060 (Fuji Film). Using Electronics Materials Co., Ltd.), paddle development was performed at room temperature for 60 seconds to form a green colored pattern on the silicon wafer substrate, and a heat treatment (post-bake) was performed for 5 minutes on a 220 ° C. hot plate.
Thus, the board | substrate which has a green coloring pattern was produced.

[Example 1]
[Preparation of red colored radiation-sensitive composition]
A colored radiation-sensitive composition of Example 1 was prepared with the following composition.
(composition)
Organic solvent: PGMEA 25.2 parts Organic solvent: EEP 1.67 parts Specific resin: B-1 below (molecular weight 18000, composition ratio is mol%) 0.74 parts Polymerizable compound: Nippon Yakuhin Co., Ltd., A-DPH-12E (C-1) 3.37 parts Photopolymerization initiator: BASF, Irgacure OXE-01 (E-2 below) 0.89 parts Pigment dispersion: R-1 63.29 parts-Fluorosurfactant: manufactured by DIC Corporation, trade name MegaFuck F-781, 0.2% EEP solution 4.17 parts-Nonionic surfactant: Takemoto Yushi Co., Ltd., Pionein D-6112-W 0.17 part UV absorber: D-0 0.50 part Polymerization inhibitor: p-methoxyphenol 0.002 part

[Formation of red pattern on silicon wafer substrate with undercoat]
On the undercoat layer of the silicon wafer substrate with the undercoat layer, the red colored radiation-sensitive composition obtained above is applied so that the dry thickness of the colored layer is about 0.8 μm, and the radiation-sensitive coloring is applied. A layer was formed. And it heat-processed for 120 second (prebaking) using the 100 degreeC hotplate. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Co., Ltd.), light having a wavelength of 365 nm is exposed to the colored layer through a 1.4 μm square island pattern mask at 400 mJ / cm ² . About 200 repetition patterns of 1 cm square were irradiated. Thereafter, the silicon wafer substrate on which the colored layer is formed is placed on a horizontal rotating table of a spin shower developing machine (DW-30 type; manufactured by Chemitronics), and an alkali developer CD-2060 (Fuji Film). Using Paddle Development for 60 seconds at room temperature using Electronics Materials Co., Ltd., a red colored pattern was formed on the silicon wafer substrate.
A silicon wafer substrate on which a red coloring pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and pure water is ejected from above the rotation center while rotating the silicon wafer substrate at a rotation speed of 800 rpm by a rotating device. It supplied from the nozzle, rinsed, and then spin-dried to obtain a color filter having a red coloring pattern.
The formed red coloring patterns were all square and had a good cross-sectional profile, indicating that the color filter was suitable for solid-state imaging devices.

[Evaluation of residue]
Using the optical wafer (manufactured by Olympus), observe the formed 1 cm square repeated pattern of the red colored silicon wafer obtained above with an objective lens 5 times, an eyepiece 10 times, and a bright field. The presence or absence of residues in the red colored pattern forming part was counted and evaluated according to the following criteria. The results are summarized in Table 4.
<Criteria>
The die ratio with residue is that a group of the same pattern was created by using a mask with a fine pattern, and 100 groups of 10 columns × 10 columns in 1 cm square were created, and residues were observed among these 100 groups. It is a group that counts and gives a percentage.

[Formation of a red colored pattern on a substrate having a green colored pattern]
The red colored radiation-sensitive composition obtained above is applied onto a silicon wafer substrate having a green colored pattern so that the thickness of the red colored layer after drying is 0.6 μm. A colored layer was formed. And it heat-processed for 120 second (prebaking) using the 100 degreeC hotplate. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), light having a wavelength of 365 nm is passed through an island pattern mask having a pattern of 1.4 μm square and 50 to 1050 mJ / cm ² . The exposure amount was changed by 50 mJ / cm ^{2 in the} range, and irradiation was performed between the green pattern and the green pattern. 200 repeated patterns were irradiated on the entire surface of the substrate. Thereafter, the silicon wafer substrate on which the colored layer is formed is placed on a horizontal rotating table of a spin shower developing machine (DW-30 type; manufactured by Chemitronics), and an alkali developer CD-2060 (Fuji Film). The paddle development is performed at room temperature for 60 seconds using Electronics Materials Co., Ltd., a red colored pattern is formed on a silicon wafer substrate having a green colored pattern, and heat treatment (post) is performed on a 220 ° C. hot plate. Bake).
In this way, a silicon wafer substrate having green and red coloring patterns was obtained.

(Linearity evaluation)
Using the electron microscope (S-9260A, manufactured by Hitachi High-Tech), the silicon wafer substrate having the green and red coloring patterns obtained above is used to form a red coloring pattern formed at an exposure amount of Eopt at a magnification of 20000 times. Observation was made, and the linearity of the edge portion of the 1.4 μm square island pattern was evaluated according to the following criteria.
Eopt is the optimum exposure amount. As the exposure amount is increased, the pattern size becomes larger than the mask, so the exposure amount is gradually increased, the pattern can be formed with the same size as the mask, and there is no peeling after development. . The results are summarized in Table 4.
<Criteria>

[Example 2]
In the preparation of the red colored radiation-sensitive composition of Example 1, the same procedure as in Example 1 was conducted except that the specific resin B-1 was changed to B-2 (the following structure: molecular weight 19000, composition ratio is mol%). A red colored radiation-sensitive composition was prepared and evaluated in the same manner as in Example 1.

Example 3
In the preparation of the red colored radiation-sensitive composition of Example 1, the red colored radiation-sensitive composition was the same as Example 1 except that the polymerizable compound C-1 was changed to C-2 (the following structure). The product was prepared and evaluated in the same manner as in Example 1.

Example 4
In the preparation of the red colored radiation-sensitive composition of Example 3, a red colored radiation-sensitive composition was prepared in the same manner as in Example 3 except that the specific resin B-1 was changed to B-2. Moreover, it evaluated similarly to Example 1. FIG.

[Examples 5 to 8]
In the preparation of the red colored radiation-sensitive composition of Example 1, the amount of the ultraviolet absorber was changed as shown in Table 4 below, and the color feelings of Examples 5 to 8 were otherwise the same as in Example 1. A radiation composition was prepared.

[Comparative Example 1]
In the preparation of the red colored radiation-sensitive composition of Example 4, a red colored radiation-sensitive composition was prepared in the same manner as in Example 4 except that the ultraviolet absorber D-1 was not added. Evaluation was conducted in the same manner as in Example 1.

[Comparative Example 2]
In the preparation of the red colored radiation-sensitive composition of Example 2, a red colored radiation-sensitive composition was prepared in the same manner as in Example 2 except that the ultraviolet absorber D-1 was not added. Evaluation was conducted in the same manner as in Example 1.

[Comparative Example 3]
In the preparation of the red colored radiation-sensitive composition of Example 3, a red colored radiation-sensitive composition was prepared in the same manner as in Example 3 except that the ultraviolet absorber D-1 was not added. Evaluation was conducted in the same manner as in Example 1.

[Comparative Example 4]
In the preparation of the red colored radiation-sensitive composition of Example 1, a red colored radiation-sensitive composition was prepared in the same manner as in Example 1 except that the ultraviolet absorber D-1 was not added. Evaluation was conducted in the same manner as in Example 1.

[Comparative Example 5]
In the preparation of the red colored radiation-sensitive composition of Example 3, the ultraviolet absorbent D-1 was not added, the specific resin B-1 was changed to B-3 (the following structure), and the others were carried out. A red colored radiation-sensitive composition was prepared in the same manner as in Example 3 and evaluated in the same manner as in Example 1.

[Comparative Example 6]
In the preparation of the red colored radiation-sensitive composition of Example 1, the ultraviolet absorber D-1 was not added, and the specific resin B-1 was changed to B-3. Similarly, a red colored radiation-sensitive composition was prepared and evaluated in the same manner as in Example 1.

Example 9
In the preparation of the red colored radiation-sensitive composition of Example 1, the polymerizable compound C-1 was changed to C-3 (the following structure), and other than that, the red colored feeling was the same as in Example 1. A radiation composition was prepared and evaluated in the same manner as in Example 1.

Example 10
In the preparation of the red colored radiation-sensitive composition of Example 1, the polymerizable compound C-1 was changed to C-4 (the following structure), and other than that, the red colored feeling was the same as in Example 1. A radiation composition was prepared and evaluated in the same manner as in Example 1.

Example 11
In the preparation of the red colored radiation-sensitive composition of Example 1, the polymerizable compound C-1 was changed to Nippon Kayaku Co., Ltd. Kayarad DPHA, and other than that, the red color was changed in the same manner as in Example 1. A colored radiation-sensitive composition was prepared and evaluated in the same manner as in Example 1.

[Comparative Example 7]
In the preparation of the red colored radiation-sensitive composition of Example 1, the amount of the ultraviolet absorber was changed as shown in Table 4 below, and the others were the same as Example 1 except that the colored radiation-sensitive property of Comparative Example 7 was used. A composition was prepared.

Table 4 shows the following.
It turns out that the Example using the coloring radiation sensitive composition containing the specific resin of this invention, a polymeric compound, and a ultraviolet absorber has the favorable linearity of a coloring pattern, and there are few residues. In particular, Examples 1, 2, and 5-8 using C-1 having an ethyleneoxy group as the polymerizable compound have good linearity of the coloring pattern. Good results were also obtained for the residue on the green pixel.

<Production of color filter>
-Preparation of blue colored radiation-sensitive composition-
The following components were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
Pigment: CIPigment Blue 15: 6 95 partsPigment derivative: 15 parts of the following compound

-Dispersant: 125 parts of the following compound (Mw35000) 30% solution-750 parts of PGMEA

  Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (manufactured by GETZMANN) using 0.3 mmφ zirconia beads to obtain a pigment dispersion (P-1). It was.

The following blue colored radiation-sensitive composition was prepared using the pigment dispersion (P-1) obtained above.
Pigment dispersion: (P-1) 1000 parts Polymerizable compound: Kayarad DPHA (manufactured by Nippon Kayaku) 100 parts Photopolymerization initiator: 1-phenyl-1,2-propanedione-2- (o-ethoxy Carbonyl) oxime 30 parts Resin: 100 parts of the above A-1 Solvent: PGMEA 300 parts

A red (R) colored pattern of 1.6 × 1.6 μm was formed on the wafer using the red colored radiation-sensitive composition of Example 6 obtained above. Furthermore, 1.6 × 1.6 μm green (G) using the green colored radiation-sensitive composition obtained in the same manner, and blue using the blue colored radiation-sensitive composition described above. The chromatic color pattern of (B) was sequentially formed to produce a color filter for a solid-state imaging device.
-Evaluation-
When a full-color color filter was incorporated into a solid-state image sensor, it was confirmed that the solid-state image sensor had high resolution and excellent color separation.

Claims (11)

(A) a colorant, (B) an acrylic resin having a partial structure represented by the following formula (I), (C) a polymerizable compound, and (D) an ultraviolet absorber, The colored radiation-sensitive composition whose content is 0.1 mass%-10 mass% with respect to solid content of a colored radiation-sensitive composition.

In formula (I), R represents a hydrogen atom or a monovalent substituent. * Represents the site of binding to the main chain structure.   The colored radiation-sensitive composition according to claim 1, wherein the acrylic resin having a partial structure represented by the formula (I) is an acrylic resin further containing a carboxyl group.   The content of the partial structure represented by the formula (I) contained in the acrylic resin having the partial structure represented by the formula (I) (B) is 1% by mass to 30% by mass with respect to the total amount of the acrylic resin. The colored radiation-sensitive composition according to claim 1 or 2.   The colored radiation-sensitive composition according to any one of claims 1 to 3, wherein the colorant (A) is a red pigment. The colored radiation-sensitive composition according to any one of claims 1 to 4, wherein the (D) ultraviolet absorber is a compound represented by the following general formula (II).

In the general formula (II), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² And do not represent hydrogen atoms at the same time. R ³ and R ⁴ each independently represents a monovalent group.   The coloring feeling according to any one of claims 1 to 5, wherein the polymerizable compound (C) is a polymerizable compound containing an ethyleneoxy group and five or more (meth) acryloyl groups in a molecule. Radiation composition.   The colored radiation-sensitive composition according to any one of claims 1 to 6, further comprising (E) a photopolymerization initiator.   The colored radiation-sensitive composition according to claim 7, wherein the (E) photopolymerization initiator is an oxime compound.   The color filter which comprises the colored film which uses the colored radiation-sensitive composition of any one of Claims 1-8. Applying the colored radiation-sensitive composition according to any one of claims 1 to 8 on a substrate to form a colored radiation-sensitive composition layer;
Exposing the colored radiation-sensitive composition layer in a pattern; and
Developing the colored radiation-sensitive composition layer after exposure to form a colored pattern; and
The manufacturing method of the color filter which has this.   A solid-state imaging device comprising the color filter according to claim 9.