KR20130032243A - Colored radiation-sensitive composition, color filter and method of producing the color filter, and solid state image sensing device - Google Patents

Abstract

PURPOSE: A coloring radiation sensitive composition, a color filter, a manufacturing method of the color filter, and a solid-state photographing device are provided to suppress generation of residue except for a color pattern formation region. CONSTITUTION: A coloring radiation sensitive composition includes a coloring agent, acrylic resin, a polymer composition and a UV absorbent. The content of the UV absorbent is 0.1 wt%-10 wt% with respect to a solid component of the coloring radiation sensitive composition.

Description

COLORED RADIATION-SENSITIVE COMPOSITION, COLOR FILTER AND METHOD OF PRODUCING THE COLOR FILTER, AND SOLID STATE IMAGE SENSING DEVICE}

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 a solid-state image sensor and a liquid crystal display. In particular, in the color filter for solid-state image sensors, the improvement of color resolving power and color reproducibility is calculated | required.

Such a color filter is provided with the colored area | region (colored cured film) of several colors, and is usually provided with the red, green, and blue colored area | region (henceforth a "colored pattern" or a "colored pixel"). Is formed. As a formation method of a coloring pattern, the coloring radiation sensitive composition which has a coloring agent of any one of red, green, and blue in a 1st color is first apply | coated on a board | substrate, and it heat-processes as needed for exposure, image development, and the said color of the said color. After forming a coloring pattern, the process of the same application | coating, exposure, image development, and heat processing as needed is repeated also in a 2nd color and a 3rd color.

As a coloring agent in a color filter, a pigment is widely used from the point which has a vivid color tone and a high coloring power, and it is preferable to use the pigment which is especially refine | miniaturized, shows preferable color and color density, and is excellent in color resolving power.

In recent years, it is required to form a fine colored pattern (for example, a colored pattern having one side of 2.0 µm or less in a solid-state imaging device) with good reproducibility for the purpose of improving the resolution in a solid-state imaging device, and at the same time the film thickness of the colored pattern Thinning (for example, 1 micrometer or less in film thickness in a solid-state image sensor) is calculated | required.

However, if the size of the colored pattern is made fine, the linearity around the rectangular colored pixel tends to be poor, and the development residue is outside the colored pattern formation region (meaning on the substrate or a pattern of a different color. The residue considered to be easy to generate | occur | produce, and for this reason, when color filter is used for a solid-state image sensor, color separation property deteriorates and it is calculated | required to overcome the fault that a solid-state image sensor with high resolution is not obtained.

Various proposals have been made to improve the linearity of colored patterns and to reduce residues. However, even with these techniques, there is still insufficient. Especially, reduction of residues generated in patterns of different colors requires further improvement of techniques. It was.

Moreover, although it is known to improve the dispersibility of a pigment using the high molecular compound which has a benzoimidazole ring as a dispersing agent of a pigment (for example, refer patent document 1), when used for a solid-state image sensor, linearity of a coloring pattern In addition, the improvement of the further technique of formation of a coloring pattern was calculated | required not the technique focused on reduction of a residue.

Japanese Patent Publication No. 2010-53307

An object of the present invention is to provide a colored radiation-sensitive composition which can form a colored pattern having good linearity and in which the occurrence of residue outside the colored pattern forming region is suppressed.

In addition, another object of the present invention is to provide a color filter having a good color pattern with good linearity and a reduced residue outside the colored pattern formation region, a method for producing the same, and a solid-state imaging device provided with the color filter.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in view of the said situation, the present inventors discovered that the said subject could be solved by the following means, and completed this invention.

Means for solving the above problems are as follows.

<1> (A) Coloring agent, (B) Acrylic resin which has partial structure represented by following formula (I), (C) polymeric compound, and (D) ultraviolet absorber are contained, Content of said (D) ultraviolet absorber The colored radiation sensitive composition which is 0.1 mass%-10 mass% with respect to solid content of this colored radiation sensitive composition.

R in formula (I) represents a hydrogen atom or a monovalent substituent. * Represents the site | part of the bond with the main chain structure of an acrylic resin.

<2> The colored radiation-sensitive composition according to <1>, wherein the content of the ultraviolet absorber (D) is 1% by mass to 5% by mass based on the solid content of the colored radiation-sensitive composition.

<3> The colored radiation-sensitive composition according to <1> or <2>, wherein the (C) polymerizable compound is a polymerizable compound containing an ethyleneoxy group and five or more acryloyl groups or methacryloyl groups in a molecule.

<4> Colored radiation-sensitive composition in any one of <1>-<3> in which the said (C) polymeric compound is represented with the following general formula (Z-1).

Six R in general formula (Z-1) are group represented by the following general formula (Z-2).

R <^1> represents a hydrogen atom or a methyl group in general formula (Z-2), m shows the number of 1 or 2, and it shows that "*" is a bond.

<5> The colored radiation-sensitive composition in any one of <1>-<4> whose acrylic resin which has the partial structure represented by said (B) Formula (I) is an acrylic resin which further contains a carboxyl group.

<6> The acrylic resin according to any one of <1> to <5>, wherein the acrylic resin having a partial structure represented by the formula (I) is at least acryloyloxyethylureylenebenzoimidazole or methacryloyl. Colored radiation-sensitive composition which is an acrylic resin derived from oxyethylureylene benzoimidazole.

<7> The acrylic resin according to any one of <1> to <6>, wherein the acrylic resin having a partial structure represented by the formula (I) is at least acryloyloxyethylureylenebenzoimidazole or methacryloyl. Colored radiation-sensitive composition which is an acrylic resin derived from oxyethylureylene benzoimidazole and acrylic acid or methacrylic acid.

<8> Content of the partial structure represented by Formula (I) contained in the acrylic resin which has a partial structure represented by said (B) Formula (I) in any one of <1>-<7> is acrylic resin Colored radiation-sensitive composition which is 1 mass%-30 mass% with respect to whole quantity.

<9> The colored radiation-sensitive composition in any one of <1>-<8> whose said (A) coloring agent is a red pigment.

<10> Colored radiation-sensitive composition in any one of <1>-<9> whose said (D) ultraviolet absorber is a compound represented by following General formula (II).

In 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 simultaneously represent a hydrogen atom There is no work. Or R ¹ and R ² together with the nitrogen atom to which R ¹ and R ² bind form a cyclic amino group. R ³ and R ⁴ each independently represent a monovalent group. Or R ³ and R ⁴ combine with each other to form a ring.

<11> The colored radiation-sensitive composition according to <10>, wherein the (D) ultraviolet absorber is a monovalent group represented by R ³ and R ⁴ in the general formula (II).

<12> The colored radiation-sensitive composition according to any one of <1> to <11>, wherein the (C) polymerizable compound is a polymerizable compound containing 3 or 4 acryloyl groups or methacryloyl groups in a molecule. .

<13> The colored radiation-sensitive composition according to any one of <1> to <12>, further comprising (E) a photopolymerization initiator.

<14> The colored radiation-sensitive composition according to <13>, wherein the photopolymerization initiator (E) is an oxime compound.

<15> The color filter provided with the colored film formed from the colored radiation-sensitive composition in any one of <1>-<14>.

<16> Process of providing the colored radiation-sensitive composition in any one of <1>-<15> on a board | substrate, and forming a colored radiation-sensitive composition layer,

Exposing the colored radiation-sensitive composition layer in a pattern;

The manufacturing method of the color filter including the process of developing the said colored radiation-sensitive composition layer after exposure, and forming a coloring pattern.

<17> The solid-state image sensor provided with the color filter as described in <16>.

The colored radiation-sensitive composition of the present invention is characterized by containing a colorant, an acrylic resin having a partial structure represented by formula (I), a polymerizable compound, and an ultraviolet absorber. Although the mechanism of improvement of the linearity of the coloring pattern in this invention and reduction of a residue is not clear, it guesses as follows. That is, in an exposure process, it is considered that the ultraviolet absorber containing the exposure light penetrating into a non-exposed part by reflection etc. in a colored radiation-sensitive composition layer is inhibited, and a latent image is considered to be formed only in an exposed part. On the other hand, in the developing step, the structure of formula (I) interacts with the colorant, and in particular, when a pigment is used as the colorant, the structural part of the formula (I) is adsorbed to the pigment and the acrylic resin is dissolved in the developer together with the colorant. It is considered to be easy to do. It is considered that the linearity of the colored pattern obtained by these actions is improved, and the residue outside the colored pattern formation region is reduced. In particular, when the compound represented by the above general formula (II) is used as the ultraviolet absorber, the variation in developing performance after the low light exposure is particularly suppressed, and thus the pattern formation properties such as the line width, the film thickness, and the spectral spectrum of the pattern are related. It is thought that the exposure roughness dependence to be suppressed can be suppressed, and the reduction of the reduction due to the addition of the ultraviolet absorber can be suppressed to improve the linearity of the colored pattern which is the effect of the present invention and to reduce the residue.

(Effects of the Invention)

According to this invention, the coloring radiation sensitive composition which can form the coloring pattern with favorable linearity and the generation | occurrence | production of the residue in other than a coloring pattern formation area can be provided can be provided.

Moreover, according to this invention, the color filter which has the coloring pattern with a good linearity, and the residue outside the colored pattern formation area was reduced, its manufacturing method, and the solid-state image sensor provided with the said color filter can be provided.

Hereinafter, the present invention will be described in detail.

Although description of the element | module described below is made | formed based on typical embodiment of this invention, this invention is not limited to this embodiment.

In the colored radiation-sensitive composition of the present invention, the total solid content refers to the total mass of components excluding the organic solvent from the total composition of the colored radiation-sensitive composition.

The numerical range represented using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In this specification, an "alkyl group" represents the alkyl group of "linear, branched, and cyclic", and may be substituted by the substituent, or may be unsubstituted.

In the present specification, the term "(meth) acrylate" refers to both or any one of acrylate and methacrylate, "(meth) acrylic" refers to both acrylate and methacrylate, ) Acryloyl "represents both or either of acryloyl and methacryloyl.

In the present specification, the terms "monomer" and "monomer" are synonyms. Monomers in the present specification are distinguished from oligomers and polymers and refer to compounds having a weight average molecular weight of 2,000 or less. In this specification, a polymeric compound means the compound which has a polymeric functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group involved in the polymerization reaction.

In addition, in description of group (atom group) in this specification, the description which is not describing substitution and unsubstitution includes what has a substituent as well as not having a substituent. For example, an "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

In the present specification, the word "process" is included in the term when the desired action of the process is achieved even if it is not clearly distinguishable from other processes as well as independent processes.

In the present invention, the term &quot; radiation &quot; means that it includes visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.

In addition, the colored area | region in the color filter of this invention includes the colored pixel (coloring pattern) area | region and light shielding film formation area | region in a color filter.

In addition, although the board | substrate which provides the colored radiation-sensitive composition of this invention is mentioned later in detail, what formed the primer layer on the photoelectric conversion element board | substrate, a silicon substrate, etc. may differ, and the pattern of a different color differs in the color of a coloring agent. Other than what was formed using the colored radiation-sensitive composition of this invention, what was formed using the colored radiation-sensitive composition different from the colored radiation-sensitive composition of this invention may be sufficient.

[Coloring radiation sensitive composition]

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

R in formula (I) represents a hydrogen atom or a monovalent substituent. * Represents the site | part of the bond with the main chain structure of an acrylic resin.

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, straight chain alkyl groups and branched alkyl groups are preferred, and methyl and ethyl groups are preferred.

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 either a pigment or a dye. Moreover, 2 or more types of pigments or 2 or more types of dyes may be sufficient as a coloring agent, and 1 or more types of pigments and 1 or more types of dyes may be used together.

The colored radiation-sensitive composition of the present invention is preferably a colored radiation-sensitive composition of red, green and blue, and is applicable to a colored radiation-sensitive composition of cyan, magenta or yellow of complementary color system. Preferably it is red, green, and blue colored radiation-sensitive composition, and when applied to a red colored radiation-sensitive composition, a large effect is obtained, and especially when applied to the colored radiation-sensitive composition using a red pigment, a larger effect is obtained. Obtained.

The coloring agent which red, green, and blue colored radiation sensitive composition contains below is demonstrated.

[Red colored radiation-sensitive composition]

The red colored radiation-sensitive composition includes pigments or dyes of red and orange. Moreover, you may contain a yellow pigment or dye. 2 or more types of red colorants may be sufficient, 2 or more types of red colorants and yellow colorants may be sufficient, a red colorant and 2 or more types of yellow colorants may be sufficient, and 2 or more types of red colorants and 2 or more types of yellow colorants may be used Also good.

As a red pigment, it is C.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

As an orange pigment, C.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 And so on.

As a red dye, it is C.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 and the like.

Among these red and orange colorants, C.I. Pigment Red 166, 177, 224, 242, 254 are preferred, in particular C.I. Pigment Red 254 is preferred.

As the yellow pigment, for example, C.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, 175, 176, 177, 179 , 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, and the like.

As a yellow dye, for example, C.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; C.I. Hood yellow 3, and the like.

Among these yellow colorants, C.I. Pigment Yellow 139 is preferred.

As content ratio of the red coloring agent and the yellow coloring agent in a red colored radiation-sensitive composition, it is preferable that it is a red coloring agent: yellow coloring agent = 80: 20-60: 40 on a mass basis, and it is especially 70:30 desirable.

In addition, it is preferable that content of all the coloring agents in red colored radiation-sensitive composition is 10%-40% on a mass basis with respect to the total solid of a red colored radiation-sensitive composition, and it is more preferable that it is 20%-30%. desirable.

[Green colored radiation-sensitive composition]

The green colored radiation-sensitive composition includes a green pigment or dye. Moreover, you may contain a yellow pigment or dye. 2 or more types of green colorants and yellow colorants may be sufficient, a green colorant and 2 or more types of yellow colorants may be sufficient, and 2 or more types of green colorants and 2 or more types of yellow colorants may be used.

As a green pigment, it is C.I. Pigment green 7, 10, 36, 37, 58 and the like.

As a green dye, for example, C.I. Acid green 1, 3, 5, 9, 16, 25, 27, 50 and the like.

Among these green colorants, C.I. Pigment green 7, 36 and 58 are preferred, in particular C.I. Pigment Greens 36 and 58 are preferred.

As the yellow pigment, for example, C.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, 175, 176, 177, 179 , 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, and the like.

As a yellow dye, for example, C.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; C.I. Hood yellow 3, and the like.

Among these yellow colorants, C.I. Pigment yellows 139, 150 and 185 are preferred.

As content ratio of the green coloring agent and yellow coloring agent in a green coloring radiation sensitive composition, it is preferable that it is green coloring agent: yellow coloring agent = 50: 50-70: 30 on a mass basis, Especially preferably, it is 60: 40.

Moreover, it is preferable that content of all the coloring agents in green colored radiation-sensitive composition is 10%-40% on a mass basis with respect to the total solid of a green colored radiation-sensitive composition, and it is more preferable that it is 20%-30%. desirable.

[Blue colored radiation-sensitive composition]

Blue colored radiation-sensitive compositions include blue pigments or dyes. In addition, a purple pigment or dye may be included. Only a blue colorant may be sufficient, 2 or more types of blue colorants and a purple colorant may be sufficient, a blue colorant and 2 or more types of purple colorants may be sufficient, and 2 or more types of blue colorants and 2 or more types of purple colorants may be used. .

As a blue pigment, it is C.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.

As a blue dye, it is C.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, and 324: 1.

Among these blue colorants, C.I. Pigment Blue 15: 3, 15: 6 are preferred, in particular C.I. Pigment Blue 15: 6 is preferred.

As a purple pigment, it is C.I. Pigment violet 1, 19, 23, 27, 32, 37, 42 and the like.

As a purple dye, for example, C.I. Acid violet 6B, 7, 9, 17, 19, C.I. Acid chromium violet K3 etc. are mentioned.

As a purple dye, the dipyrromethene dye represented by general formula (M) mentioned later is also preferable.

[Dipyrromethene Dye = Specific Dye Represented by General Formula (M)]

It is preferable that the blue pixel in this invention contains the dipyrromethene dye represented by the following general formula (M) (henceforth "a specific dye" suitably).

As said specific dye, what is necessary is just the dipyrromethene dye represented by the following general formula (M), and the structure derived from the dipyrromethene metal complex compound obtained from general formula (M) and a metal or a metal compound, or its tautomer.

R ⁴ to R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent. Provided that R ⁴ and R ⁹ are not bonded to each other to form a ring]

As a dipyrromethene metal complex compound or its tautomer obtained from the dipyrromethene compound represented by the said general formula (M) and a metal or a metal compound, it is specifically represented by following General formula (5) or following General formula (6). A dipyrromethene metal complex compound is mentioned.

However, this invention is not limited to these.

(Dipyrromethene Metal Complex Compound Represented by General Formula (5))

In said general formula (5), R <^4> -R <^9> represents a hydrogen atom or a substituent each independently, 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 group which can couple | bond with Ma, X <^2> represents group which neutralizes the charge of Ma, X <^1> and X <^2> may combine with each other, and may form the 5-membered, 6-membered, or 7-membered ring with Ma. However, R ⁴ and R ⁹ do not combine with each other to form a ring. In addition, the dipyrromethene metal complex compound represented by the said General formula (5) contains tautomers.

Although it does not specifically limit as a site | part from which one or two hydrogen atoms isolate | separate from the dipyrromethene metal complex compound represented by said General formula (5) in order to comprise a pigment | dye residue, Any one of R <^4> -R <^9> from the point of synthetic compatibility. Dogs or two sites are preferred, any one or two sites of R ⁴ , R ⁶ , R ⁷ and R ⁹ are more preferred, and one or two sites of R ⁴ and R ⁹ are even more preferred. .

It is preferable that the specific dye in this invention has alkali-soluble group.

When using the dye monomer or structural unit which has an alkali-soluble group as a method of introduce | transducing an alkali-soluble group into a specific dye, in R <^4> -R <^10> , X <^1> , X <^2> of the dipyrromethene metal complex compound represented by said General formula (5). Any one or two or more substituents may have an alkali-soluble group. Among these substituents, any one of R ⁴ to R ⁹ and X ¹ is preferable, any one of R ⁴ , R ⁶ , R ⁷ and R ⁹ is more preferable, and one of R ⁴ and R ⁹ is still more preferable.

The dipyrromethene metal complex compound represented by the said General formula (5) may have functional groups other than alkali-soluble group, unless the effect of this invention is impaired.

(Dipyrromethene Metal Complex Compound Represented by General Formula (6))

R ¹¹ and R ¹⁶ in the general formula (6) each independently represent 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. R ¹² to R ¹⁵ each independently represent 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 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, an oxygen atom or 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. 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 may be bonded to each other to form a 5-, 6-, or 7-membered ring. X ¹ represents a group capable of bonding with Ma, and a represents 0, 1 or 2. In addition, the dipyrromethene metal complex compound represented by the said General formula (6) contains tautomers.

From C. difficile Romero ten metal complex compound represented by the general formula (6) in order to configure a pigment moiety as the region to be separated one or two hydrogen atoms are particularly limited, but ^{R 11 ~ R 17, X 1} , Y 1 ~ Y which of the ^two is one or two parts.

Among these, any one or two sites of R ¹¹ to R ¹⁶ and X ¹ are preferable in view of synthetic suitability, and more preferably any one or two sites of R ¹¹ , R ¹³ , R ¹⁴ and R ¹⁶ . More preferably one or two sites of R ¹¹ and R ¹⁶ .

R ¹¹ ~ of the present invention, when a method of introducing an alkali-soluble group to a specific dye for a dye monomer or a structural unit having an alkali-soluble group represented by the formula (6) Diffie Romero ten metal complex compound according to R ^17, X ^1, Y ¹ ~ Y may be provided with an alkali-soluble group in any of the ²¹ or more than two substituents. Among these substituents, any one of R ¹¹ to R ¹⁶ and X ¹ is preferable, any one of R ¹¹ , R ¹³ , R ¹⁴ and R ¹⁶ is more preferable, and any one of R ¹¹ and R ¹⁶ is still more preferable.

The dipyrromethene metal complex compound represented by the said General formula (6) may have functional groups other than alkali-soluble group, unless the effect of this invention is impaired.

Dipyrromethene metal complex compounds represented by the general formulas (5) and (6) are U.S. Patent Nos. 4,774,339, 5,433,896, Japanese Patent Laid-Open No. 2001-240761, 2002-155052, Japan It can be synthesize | combined by the method of patent No. 3614586, Aust. J. Chem, 1965, 11, 1835-1845, JH Boger et al, Heteroatom Chemistry, Vol. 1, No. 5, 389 (1990) etc. Specifically, Paragraph 0131 of Unexamined-Japanese-Patent No. 2008-292970-the method of 0157 can be applied.

It is preferable that the specific dye in this invention is a dye multimer containing a dipyrromethene structure, and the pigment | dye site | part in the dye multimer containing a dipyrromethene structure is represented by said general formula (M) It is preferable that it is a structure derived from the dipyrromethene metal complex compound obtained from a compound and a metal or a metal compound, or its tautomer.

In addition, as a dipyrromethene metal complex compound or tautomer obtained from the dipyrromethene compound represented by the general formula (M) and the metal or metal compound, the dipy represented by the general formula (5) or the general formula (6) Lomethene metal complex compounds are preferred.

Next, a dye multimer is demonstrated.

Although it is preferable that the specific dye in this invention is a dye multimer containing a dipyrromethene structure, it is preferable that weight average molecular weights (Mw) are 5,000 or more and 20,000 or less, More preferably, they are 5,000 or more and 16,000 or less, More preferably, It is 6,000 or more and 12,000 or less.

When a weight average molecular weight (Mw) is less than 5,000, when it is set as a blue pixel, there exists a tendency for the thermal diffusion (color stain) of the coloring agent by heat processing, the penetration of a coloring agent, alkali elution resistance, and solvent resistance to deteriorate. When the weight average molecular weight exceeds 20,000, the developing residues tend to be particularly deteriorated.

Moreover, as dispersion degree (weight average molecular weight / number average molecular weight Mw / Mn), it is preferable that they are 1.00 or more and 2.50 or less.

When Mw / Mn exceeds 2.50, when it is set as a colored film, there exists a tendency for the thermal diffusion (color stain) of the coloring agent by heat processing, the penetration of a coloring agent, alkali elution resistance, and solvent resistance to deteriorate. Mw / Mn needs to be 1.00 or more and 2.50 or less, Preferably they are 1.00 or more and 2.20 or less, More preferably, they are 1.00 or more and 2.00 or less.

In addition, the weight average molecular weight and molecular weight distribution (Mw / Mn) were measured using gel permeation chromatography (GPC) using HLC-8220GPC (developed solvent NMP, detection RI, polystyrene conversion value) manufactured by Tosoh Corporation. Indicates a value.

It is preferable that the specific dye in this invention has alkali-soluble group.

As an alkali-soluble group, a carboxyl group, a phosphono group, a sulfo group, etc. are mentioned. Especially, a carboxyl group is preferable.

It is preferable that the acid value of a specific dye is 0.5 mmol / g or more and 3.0 mmol / g or less, It is more preferable that it is 0.6 mmol / g or more and 2.5 mmol / g or less from a viewpoint of using preferably by the photolithographic method mentioned later. It is especially preferable that they are 0.7 mmol / g or more and 2.0 mmol / g or less.

Specific dyes in the present invention include dimers, trimers, oligomers, polymers, and the like.

When synthesize | combining a dye multimer by a copolymerization reaction, if a comonomer can superpose | polymerize with a polymeric dye monomer, there will be no limitation in particular.

These comonomers include styrene-based compounds, unsaturated carboxylic acid monomers and their esters, amides, imides or anhydrides, and vinyl compounds.

Examples of styrene 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, 1-butyne-2,3,4-tricarboxylic acid.

Examples of esters of unsaturated carboxylic acids include methyl esters of the α, β-unsaturated carboxylic acids, ethyl esters, 2-hydroxyethyl esters, propyl esters, butyl esters, octyl esters, dodecyl esters, 2,2, 6,6-tetramethyl-4-piperidyl ester, 1,2,2,6,6-pentamethyl-4-piperidyl ester, 2- [3- (2-benzotriazolyl) -4-hydrate Oxyphenyl] ethyl ester.

Examples of the amide of the unsaturated carboxylic acid include methylamide, dimethylamide, ethylamide, diethylamide, propylamide, dipropylamide, butylamide, dibutylamide, hexylamide of the α, β-unsaturated carboxylic acid, Octylamide, phenylamide and the like.

Examples of the imide of unsaturated carboxylic acid are maleimide, itaciconimide, N-butyl maleimide, N-octyl maleimide and N-phenylmaleimide. Examples of vinyl compounds are vinyl acetate, N-vinylcarbazole and N-vinylpyrrolidone.

Although the copolymerization ratio of a polymeric pigment monomer and a comonomer changes with kinds of polymeric pigment monomer, it is preferable that it is a ratio of comonomer 5-10000g with respect to 100g of a polymeric pigment monomer normally, and it is more preferable that it is a ratio of comonomer 51000g. It is preferable and it is especially preferable that it is the ratio of 5-100 g of comonomers.

(Dye monomer represented by general formula (1))

It is also preferable that the specific pigment | dye in this invention superposes | polymerizes and is obtained by superposing | polymerizing the pigment | dye monomer containing the dipyrromethene structure represented by following General formula (1).

R <^1> in the said General formula (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 (= 0) N (R ² )-, -C (= 0) O-, the following general formula ( The group represented by 2), group represented by following General formula (3), or group represented by following General formula (4) is shown. L ² represents a divalent linking group. m and n each independently represent 0 or 1. Dye represents a pigment residue including a dipyrromethene structure. R ² represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

R <^2> represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group here. R ³ represents a hydrogen atom or a substituent. k represents the integer of 0-4, and when k is 2 or more, R <^3> may be same or different. In General Formulas (2) to (4), * represents a position to bond with a -C (R ¹ ) = CH ₂ group in the general formula (1), and ** represents a general formula (1). Where L ² or Dye (if n = 0).

That is, the dye monomer containing the dipyrromethene structure represented by the general formula (1) is represented by-(L ² ) _n- (L ¹ ) _m -C (R ¹ ) = to the dye compound containing the dipyrromethene structure. represented by CH ₂ is a compound in which the polymerizable group is introduced.

In addition, when both m and n are 0, a -C (R ¹ ) = CH ₂ group is introduced directly into the dye compound containing a dipyrromethene structure.

In the general formula (1), when R ¹ is an alkyl group or an aryl group, unsubstituted or substituted.

When said R <^1> is an alkyl group, Preferably it is C1-C36, More preferably, a C1-C6 substituted or unsubstituted linear, branched or cyclic alkyl group 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 said R <^1> is an aryl group, Preferably it is 6-18 carbon atoms, More preferably, it is 6-14 carbon atoms, More preferably, a C6-C12 substituted or unsubstituted aryl group is preferable. A phenyl group, a naphthyl group, etc. are mentioned as an example of an aryl group.

Substituents when R ¹ is a substituted alkyl group or a substituted aryl group include a halogen atom (for example, fluorine, chlorine, bromine and iodine) and an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms). Alkyl group, for example methyl, ethyl, propyl, butyl, isopropyl, t-butyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, adamantyl), aryl group (preferably carbon number) 6 to 24, more preferably an aryl group having 6 to 12 carbon atoms, for example, phenyl and naphthyl), a heterocyclic group (preferably having 1 to 24 carbon atoms, more preferably a heterocyclic group having 1 to 12 carbon atoms). 2-thienyl, 4-pyridyl, 2-pril, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazole -1-yl), silyl group (preferably a silyl group having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms) For example, trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group, nitro group, sulfonic acid group, phosphonic acid group, carboxyl group, alkoxy group (preferably It is a C1-C24, More preferably, it is a C1-C12 alkoxy group, More preferably, it is a C1-C6 alkoxy group, For example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopro It is a foxy, t-butoxy, dodecyloxy, cycloalkyloxy group, for example cyclopentyloxy, cyclohexyloxy), an aryloxy group (preferably C6-C24, More preferably, C6-C6) 12 aryloxy groups, for example, phenoxy, 1-naphthoxy), heterocyclic oxy group (preferably 1 to 24 carbon atoms, more preferably heterocyclic oxy group) 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), silyloxy group (bar Preferably it is a C1-C24 silyloxy group, More preferably, it is a C1-C12 silyloxy group, For example, trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably Is an acyloxy group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, an acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy) and an alkoxycarbonyloxy group (preferably An alkoxycarbonyloxy group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms, for example, ethoxycarbonyloxy, t-butoxycarbonyloxy), Cycloalkyloxycarbonyloxy (for example, cyclohexyloxycarbonyloxy), aryloxycarbonyloxy group (preferably having 7 to 24 carbon atoms, more preferably 7 to 12 carbon atoms) It is a silyloxy group, for example, phenoxycarbo Nyloxy) and a carbamoyloxy group (preferably a carbamoyloxy 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- Dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy), sulfamoyloxy group (preferably 1 to 24 carbon atoms, more preferred) Preferably it is a sulfamoyloxy group of 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, for example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy, alkylsulfonyloxy group (preferably Is an alkylsulfonyloxy group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, and for example, methylsulfonyloxy, hexadecylsulfonyloxy, and cyclohexylsulfonyl Oxy), an arylsulfonyloxy group (preferably C6-C24, More preferably Is an arylsulfonyloxy group having 6 to 12 carbon atoms, for example, phenylsulfonyloxy, an acyl group (preferably an acyl group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms), for example, Wheat, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl),

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, for example, methoxycarbonyl, ethoxycarbonyl, octade Siloxycarbonyl, cyclohexyloxycarbonyl), aryloxycarbonyl group (preferably aryloxycarbonyl group having 7 to 24 carbon atoms, more preferably 7 to 12 carbon atoms, for example, phenoxycarbonyl), carbon Bamoyl group (preferably a carbamoyl group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, for example, carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octyl Carbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methyl-N-phenylcarbamoyl, N, N-dicyclohexylcarbamoyl) , Amino group (preferably 24 or less carbon atoms, more preferably 12 or less carbon atoms) It is an amino group of, for example, amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino), an anilino group (preferably 6 to 24 carbon atoms, more preferred) Preferably it is a C6-C12 aniline group, For example, an anilino, N-methylanilino, heterocyclic amino group (preferably C1-C24 heterocyclic amino group) For example, 4-pyridylamino) and a carbonamide group (preferably a C2-C24, more preferably a C2-C12 carbonamide group), For example, acetamide, benzamide, tetradecane Amide, pivaloylamide, cyclohexaneamide), ureido group (preferably ureido group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms), for example, ureido, N, N-dimethyl ureido , N-phenylureido), Mid group (preferably C20 or less, More preferably, it is C12 or less imide group, For example, N-succinimide, N-phthalimide), Alkoxycarbonylamino group (Preferably carbon number It is 2-24, More preferably, it is a C2-C12 alkoxycarbonylamino group, For example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino , Cyclohexyloxycarbonylamino), aryloxycarbonylamino group (preferably aryloxycarbonylamino group having 7 to 24 carbon atoms, more preferably 7 to 12 carbon atoms, for example, phenoxycarbonylamino) And sulfonamide groups (preferably sulfonamide groups having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms), for example, methane sulfonamide, butane sulfonamide, benzene sulfonamide, and hexadecane sulfona. Mead, cyclohexanesulfonamide), sulfamoylamino group (preferably a sulfamoylamino group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms), for example, N, N-dipropylsulfamoylamino and 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-pyrazolyl azo), alkylthio group (Preferably an alkylthio group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, for example, methylthio, ethylthio, octylthio, cyclohexylthio) and an arylthio group (preferably C6) To 24, more preferably an arylthio group having 6 to 12 carbon atoms, for example, phenylthio) and a heterocyclic thi group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms). Thiogi, for example 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, for example dodecanesulfinyl),

An arylsulfinyl group (preferably C6-C24, More preferably, it is a C6-C12 arylsulfinyl group, for example, phenylsulfinyl), an alkylsulfonyl group (preferably C1-C24), More preferable Preferably it is a C1-C12 alkylsulfonyl group, For example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsul Fonyl, cyclohexylsulfonyl), arylsulfonyl group (preferably arylsulfonyl group having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, for example, phenylsulfonyl, 1-naphthylsulfonyl), sulf Pamoyl group (preferably a sulfamoyl group having 24 or less carbon atoms, more preferably 16 or less carbon atoms), for example sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl , N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo groups, phospho A nilyl group (preferably a phosphonyl group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms), for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl) and phosphinoylamino group (preferably Is a C1-C24, More preferably, it is a C1-C12 phosphinoylamino group, For example, diethoxy phosphinoylamino and dioctyloxy phosphinoylamino) are mentioned.

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, aryloxy carbo Neyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carbonamide group, imide group, sulfonamide group, sulfamoylamino group , Sulfamoyl group is preferable, and an alkyl group, an aryl group, 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, and a carba Moyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carbonamide group, sulfonamide group, sulfa One amino group and sulfamoyl group are more preferable, and a hydroxyl group, sulfonic acid group, phosphonic acid group, carboxylic acid group, alkoxy group, aryloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group , Sulfamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group are more preferable, and hydroxyl group, sulfonic acid group, carboxylic acid group, alkoxy group, alkoxycarbonyloxy group, carbon Bamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, acyl group, and alkoxycarbonyl group are particularly preferable.

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

In said general formula (1), as R <^1> , a hydrogen atom, an alkyl group, and an aryl group are preferable, and a hydrogen atom and an alkyl group are especially preferable.

If the case the general formula (1) of the more substitutable group substituent of the substituted alkyl group and substituted aryl group of R ¹ is may be substituted with substituents described above and is substituted by two or more substituents include their substituents may be the same It may be different.

In Formula (1), L ¹ is -N (R ² ) C (= O)-, -OC (= O)-, -C (= O) N (R ² )-, -C (= O) O-, group represented by following General formula (2), group represented by General formula (3), or group represented by General formula (4) are represented. R <^2> represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group here.

In the general formula (1), the alkyl group, aryl group and heterocyclic group of R ² may be exemplified by the alkyl group, aryl group and heterocyclic group described in the substituent of the substituted alkyl group and substituted aryl group of R ¹ , and the preferred form is also the same. to be.

Alkyl group, aryl group and heterocyclic group in the R ² may have their substituents may be the same or different when it is substituted with a substituent may be substituted with a substituent, two or more described in the R ^1.

The group represented by following General formula (2) represented by L <^1> in the said General formula (1), the group represented by General formula (3), and the group represented by General formula (4) are demonstrated below.

R <^2> represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group here, R <^3> represents a hydrogen atom or a substituent, k represents the integer of 0-4, and when k is two or more, R <^3> may be same or different. * Represents a position to bond with the group -C (R ¹ ) = CH ₂ in the formula (1), and ** represents L ² or Dye in the formula (1) (when n = 0). Indicates the position to join with.

Wherein R ² is R ² and accept the above-described formula (1), the preferred form is also the same.

Said R <^3> represents a hydrogen atom or a substituent, As a substituent represented by R <^3> , the substituent demonstrated by the substituted alkyl group and substituted aryl group of said R <^1> can be mentioned as an example, and a preferable aspect is also the same. k represents 0, 1, 2, 3, 4. When k is 2, 3, or 4, R <^3> may be the same and may differ.

When the substituent of R <^3> is a group which can be substituted further, it may be substituted by the substituent demonstrated by said R <^1> , and when substituted by two or more substituents, those substituents may be same or different.

The -N from the viewpoint of synthesis as ^{L 1 (R 2) C (} = O) -, -OC (= O) -, -C (= O) N (R 2) -, -C (= O) O- Is preferable, -OC (= 0)-, -C (= 0) N (R ² )-, -C (= 0) O-, and -C (= 0) N (R ² )- , -C (= 0) O- is more preferred.

Next, L <^2> in the said General formula (1) is demonstrated.

L ² represents a divalent linking group connecting D ¹ to an L ¹ or —C (R ¹ ) ═CH ₂ group (when m = 0).

L ² is preferably an alkylene group, an aralkylene group, an arylene group, -O-, -C (= 0)-, -OC (= 0)-, OC (= 0) 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-, -SS-,- _{SO-, -SO 2 -, -SO 2} N (R 50) -, -SO ₂ O-, etc. may be mentioned. In addition, a plurality of divalent couplers may be bonded to form a divalent coupler.

R ⁵⁰ and R ⁵¹ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. The alkyl group, aryl group, and heterocyclic group of R ⁵⁰ and R ⁵¹ may be exemplified by the alkyl group, aryl group, and heterocyclic group described by the substituent of R ¹ , and the preferred form is also the same. The alkyl group, aryl group, and heterocyclic group of R ⁵⁰ and R ⁵¹ may be substituted with the substituent described by the substituent of R ¹ above, and when substituted with two or more substituents, those 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 may be substituted. When substituted, the substituent may be substituted with the substituents described by the substituents of R ¹ and substituted with two or more substituents. If it is, those substituents may be the same or different.

When L <^2> is an alkylene group, an aralkylene group, or an arylene group, a C1-C12 alkylene group, a C6-C18 aralkylene group, a C6-C18 arylene group is preferable, and a C1-C8 alkylene group More preferably, a C6-C16 aralkylene group and a C6-C12 arylene group are more preferable, A C1-C6 alkylene group and a C6-C12 aralkylene group are more preferable.

As a combination of L ¹ and L ² , L ¹ represents —N (R ² ) C (═O) —, —OC (═O) —, —C (═O) N (R ² ) —, —C (= O) O-, L ² is an alkyl 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, and an alkyl carbon having 2 to 18 carbon atoms. The form of an amide group and a C2-C18 alkylaminocarbonyl group is preferable. More preferably, L ¹ is -OC (= O)-, -C (= O) N (R ² )-, -C (= O) O-, and L ² is a C1-C8 alkylene group or carbon number 6 to 16 aralkylene groups, arylene groups having 6 to 12 carbon atoms, alkylthioethers having 2 to 12 carbon atoms, alkylcarbonamide groups having 2 to 12 carbon atoms, and alkylaminocarbonyl groups having 2 to 12 carbon atoms, more preferably. Is L ¹ is -C (= O) N (R ² )-, -C (= O) O-, L ² is an alkylene group of 1 to 6 carbon atoms, an aralkylene group of 6 to 12 carbon atoms, or 2 to It is a form of six alkylthio ethers, a C2-C6 alkylcarbonamide group, and a C2-C6 alkylaminocarbonyl group.

In the above general formula (1) to-give you one example of the polymerizable group represented by _{^{(L 1) m -C (R}} 1) = CH 2 - (L 2) n. However, the present invention is not limited thereto.

(Example Compounds of Specific Dyes)

Although the exemplary compound of the specific dye in this invention is shown below, this invention is not limited to the following exemplary compound at all.

In addition, in the following exemplary compound, "wt-%" is a mass reference | standard.

In addition, in Exemplary Compounds 2-1 to 2-5, polymerization is carried out in accordance with the ratios of the structural components constituting the composition ratio a and the methacrylic acid component corresponding to the composition ratio (b + c) in the table. Part of the methacrylic acid component of the dye multimer generated by the polymerization is coordinated to Zn by the equimolar amount with the constituent component constituting the composition ratio a.

As a content ratio of the blue coloring agent and purple coloring agent in a blue colored radiation sensitive composition, it is preferable that it is a blue coloring agent: purple coloring agent = 80: 20-60: 40 on a mass basis, and it is especially 70:30 desirable.

Moreover, it is preferable that content of all the coloring agents in a blue colored radiation sensitive composition is 10%-40% by mass basis with respect to the total solid of a blue colored radiation sensitive composition, and it is more preferable that it is 20%-30%. desirable.

In addition, as a colorant, direct dyes, basic dyes, mordant dyes, acidic mordant dyes, azoic dyes, disperse dyes, useful dyes, food dyes and / or derivatives thereof, and the like can also be usefully used.

Moreover, the azo-type, xanthene type, and phthalocyanine-type acid dye of that excepting the above is also preferable, and C.I. Solvent blue 44, 38; C.I. Solvent orange 45; Acid dyes such as rhodamine B and rhodamine 110 and derivatives of these dyes are also preferably used.

Especially, as dye, triaryl methane type, anthraquinone type, azomethine type, benzylidene type, oxonol type, cyanine type, phenothiazine type, pyrrolopyrazole azomethine type, xanthene type, phthalocyanine type, benzopyran type, indigo It is preferable that it is a dye chosen from a system, a pyrazole azo system, an anilino azo system, a pyrazolotriazole azo system, a pyridone azo system, an anthrapyridone system, and a pyrromethene system.

In addition, the dye may be a multimer.

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

As a pigment applied to the colored radiation-sensitive composition of the present invention, it is preferable that the color filter obtained by applying the colored radiation-sensitive composition of the present invention is preferably of high color purity, and as fine as possible. Moreover, when the handling property of a colored radiation-sensitive composition is also considered, 5 nm-100 nm are preferable and, as for the average primary particle diameter of a pigment, 5 nm-50 nm are more preferable.

In the colored radiation-sensitive composition of each color, an appropriate chromaticity is obtained when the color filter is produced by the colored radiation-sensitive composition by setting the content of the colorant to the respective ranges described above. Moreover, since radiation hardening fully advances and the intensity | strength as a colored cured film can be maintained, the developing latitude at the time of alkali image development can be prevented from narrowing.

When using a pigment as a coloring agent (A) in the coloring radiation-sensitive composition of this invention, a pigment is previously disperse | distributed with a pigment dispersant, an organic solvent, other components, etc. as needed, the pigment dispersion liquid is prepared, and the obtained pigment dispersion liquid is (B) It is preferable to mix and prepare with specific resin, (C) polymeric compound, (D) ultraviolet absorber, and the other component added as needed.

The composition of a pigment dispersion liquid and the method of preparation of a pigment dispersion liquid are demonstrated in detail below.

In this invention, a pigment may prepare a pigment dispersion liquid separately, respectively, or may arrange a pigment dispersion liquid 2 types, 3 types, or 4 or more together.

When setting it as 2 or more types of pigment dispersion liquid, the composition other than the pigment of a pigment dispersion liquid, and the preparation method of a pigment dispersion liquid may be same or different.

The method for preparing the pigment dispersion is not particularly limited, but as a method of dispersion, for example, a bead disperser using zirconia beads or the like, which is previously mixed with a pigment and a pigment dispersant and dispersed in advance by a homogenizer or the like (for example, manufactured by GETZMANN Co., Ltd.) Dispermat) or the like and fine dispersion.

(Pigment dispersant)

As a pigment dispersant which can be used in the present invention, a polymeric dispersant [for example, polyamideamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylic Acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate] and surfactants such as polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine, and pigment derivatives.

Polymeric dispersants can be further divided into linear polymers, end-modified polymers, graft-type polymers, and block-type polymers from the structure.

As a terminal modified type polymer which has an anchor part to a pigment surface, For example, the polymer which has a phosphoric acid group at the terminal described in Unexamined-Japanese-Patent No. 3-112992, 2003-533455, etc., Unexamined-Japanese-Patent No. 2002-273191 The polymer which has a sulfonic acid group at the terminal described in the publication, etc., The polymer which has the partial skeleton and heterocycle of the organic pigment of Unexamined-Japanese-Patent No. 9-77994, etc. are mentioned. Further, a polymer having an anchor moiety (an acid group, a basic group, a partial skeleton of an organic dye, a heterocycle, etc.) introduced into two or more pigment surfaces at the polymer terminal described in Japanese Patent Application Laid-Open No. 2007-277514 is also excellent in dispersion stability desirable.

Examples of the graft polymer having an anchor portion to the pigment surface include poly (lower alkyleneimines described in Japanese Patent Application Laid-Open No. 54-37082, Japanese Patent Application Laid-open No. Hei 8-507960, Japanese Patent Application Laid-Open No. 2009-258668, and the like. ), A reaction product of a polyester, a reaction product of a polyallylamine and a polyester described in JP-A-9-169821, etc., a macromonomer described in JP-A-10-339949, JP-A-2004-37986, etc. Graft polymer having a partial skeleton and heterocycle of an organic pigment as described in Copolymer of a nitrogen atom monomer, Japanese Patent Application Laid-Open No. 2003-238837, Japanese Patent Application Laid-Open No. 2008-9426, Japanese Patent Application Laid-Open No. 2008-81732, etc. The copolymer of the macromonomer and acid-group containing monomer etc. which were described in Unexamined-Japanese-Patent No. 2010-106268 etc. are mentioned. In particular, the amphoteric dispersing resin having a basic group and an acidic group described in JP-A-2009-203462 is particularly preferable from the viewpoints of dispersibility, dispersion stability, and developability of the colored radiation-sensitive composition of the pigment dispersion.

As a macromonomer used when producing a graft type polymer having an anchor site to the pigment surface by radical polymerization, a known macromonomer can be used, and macromonomer AA-6 manufactured by Toagosei Co., Ltd. (terminal group is methacryl) Dimethylmethyl methacrylate, AS-6 (polystyrene whose terminal group is methacryloyl group), AN-6S (copolymer of styrene and acrylonitrile whose terminal group is methacryloyl group), AB-6 (terminal group Butyl polyacrylate which is a methacryloyl group), Flaccel FM5 (the 5 molar equivalent addition of epsilon -caprolactone of 2-hydroxyethyl methacrylate) made from Daicel Kagaku Kogyo Co., Ltd., FA10L (2-hydroxy acrylate) 10 mol equivalents of (epsilon) -caprolactone adduct of oxyethyl), the polyester-type macromonomer of Unexamined-Japanese-Patent No. 2-272009, etc. are mentioned. Among them, a polyester macromonomer having excellent flexibility and affinity for solvents is particularly preferred from the viewpoints of dispersibility, dispersion stability of the pigment dispersion, and developability exhibited by the colored radiation-sensitive composition using the pigment dispersion, and furthermore, Most preferred is a polyester-based macromonomer represented by the polyester-based macromonomer described in -272009.

As block type polymers having anchor sites to the pigment surface, block type polymers described in JP-A-2003-49110 and JP-A-2009-52010 are preferable.

The pigment dispersant which can be used for this invention can also be obtained as a commercial item, As such a specific example, "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 made by BYK Chemie. (Polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)," EFKA4047, 4050-4010-made by EFKA " 4165 (Polyurethane), EFKA4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (Phthalocyanine derivative), 6750 (azo pigment derivative), "Azispa PB821, PB822, PB880, PB881" made by Ajinomoto Fine Techno Co., Ltd., "Florene TG-710 (urethane oligomer)" by Kyowa Co., Ltd., "Polyflo No.50E, No.300 (Acrylic Copolymer), Katsumoto Kasei "Disparon KS-860, 873SN, 874, # 2150 (aliphatic polyhydric carboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725", "demolable" RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate), "homogenol L-18 (polymeric polycarboxylic acid)", "emulgen 920, 930, 935 , 985 (polyoxyethylene nonyl phenyl ether), "acetamine 86 (stearylamine acetate)", "Solpers 5000 (phthalocyanine derivative)", 22000 (azo pigment derivative), 13240 (made by Nippon Lubrizol Co., Ltd.) Polyester amine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) '', Nikko T106 (polyoxyethylene sorbitan monooleate) manufactured by Nikko Chemical, Product made by Shin-Etsu Kagaku Kogyo Co., Ltd. such as MYS-IEX (polyoxyethylene monostearate), Hinoakuto T-8000E made by Kawaken Fine Chemicals Co., Ltd. Kanosiloxane polymer KP341, Yusho Corporation "W001: cationic surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene Nonionic surfactants, such as nonylphenyl ether, polyethyleneglycol dilaurate, polyethyleneglycol distearate, and sorbitan fatty acid ester, anionic surfactant, such as "W004, W005, W017", and Morishita Sangyo Co., Ltd. product "EFKA" -46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 '', Dispersade 6, Disperse Ade 8, Disperse Ade 15 Polymer dispersing agent such as "Disperse Ade 9100", "ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, made by ADEKA Co., Ltd. P103, F108, L121, P-123 "and Sanyo Kasei Co., Ltd." Ionet S-20 ", "Accre cure RD-F8" by Nippon Shokubai, "Accre base FFS-6824" by Fujikura Kasei, etc. are mentioned.

These pigment dispersants may be used independently and may be used in combination of 2 or more type. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymeric dispersant. Moreover, it is preferable that the pigment dispersant in this invention is a terminal modified | denatured type | mold polymer | macromolecule, a graft type polymer, and a block type polymer which have an anchor site | part to the said pigment surface.

As content of the pigment dispersing agent 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, It is further more preferable that it is 10-60 mass parts.

Specifically, in the case of using a polymer dispersant, the amount thereof is preferably in the range of 5 to 100 parts, more preferably in the range of 10 to 80 parts, in terms of mass with respect to 100 parts by mass of the pigment.

Pigment Derivatives

The pigment dispersion preferably further contains a pigment derivative.

A pigment derivative is a compound which has a structure which substituted a part of organic pigment with an acidic group, a basic group, or a phthalimide methyl group. It is preferable to contain a pigment derivative which has an acidic group or a basic group from a viewpoint of dispersibility and dispersion stability as a pigment derivative.

As organic pigments for constituting the pigment derivative, diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments And isoindolin pigments, isoindolinone pigments, quinophthalone pigments, indanthrene pigments, and metal complex pigments.

Moreover, as an acidic group which a pigment derivative has, 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. As a basic group which a pigment derivative has, an amino group is preferable and tertiary amino group is especially preferable.

Especially as a pigment derivative, the pigment derivative of quinoline type, benzimidazolone type, and isoindolin type is preferable, and the pigment derivative of quinoline type and benzimidazolone type is more preferable. In particular, the pigment derivative which has a structure represented by the following general formula (P) is preferable.

In general formula (P), A represents the partial structure chosen from the following general formula (PA-1) (PA-3)-. B represents a single bond or a (t + 1) valent coupling group. C represents a single bond, -NH-, -CONH-, -CO _2- , -SO ₂ NH-, -O-, -S- or -SO _2- . 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 the integer of 1-5.

R <_p1> in general formula (PA-1) and (PA-2) represents a C1-C5 alkyl group or an aryl group. R <_p2> in general formula (PA-3) represents a hydrogen atom, a halogen atom, an alkyl group, or a hydroxyl group. s represents the integer of 1-4. R _p3 in Formula (PA-1) and Formula (PA-3) is a single bond, -NH-, -CONH-, -CO _2- , -SO ₂ NH-, -O-, -S- or- SO ₂ -is represented. * Denotes the connection with B

In general formula (P), R <_p1> has a methyl group or a phenyl group especially preferable, and a methyl group is the most preferable. 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.

Examples of the (t + 1) valent linking group represented by B in General Formula (P) include an alkylene group, a cycloalkylene group, an arylene group, and a heteroarylene group. Among them, the linking group represented by the following structural formulas (PA-4) to (PA-9) is particularly preferable.

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

As the alkylene group, cycloalkylene group, and arylene group represented by D in General Formula (P), for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, decylene, cyclopropylene, cyclobutylene, cyclophene Tylene, cyclohexylene, cyclooctylene, cyclodecylene, phenylene, naphthylene, etc. are mentioned. Among these, as D, an alkylene group is especially preferable, and C1-C5 alkylene is the most preferable.

When E in formula (P) represents -N (Rpa) (Rpb), examples of the alkyl group, cycloalkyl group and aryl group in Rpa and Rpb include methyl, ethyl, propyl, isopropyl, butyl, sec- Butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, octyl, decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, phenyl, naphthyl and the like. Especially as Rpa and Rpb, an alkyl group is preferable and a C1-C5 alkyl group is the most preferable. 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 1 type may be used for a pigment derivative and it may use 2 or more types together.

Moreover, when using a pigment derivative together, it is preferable that it is in the range of 1-30 parts in mass conversion with respect to 100 mass parts of pigments as a usage-amount of a pigment derivative, It is more preferable to exist in the range of 3-20 parts, The range of 5-15 parts It is particularly preferred to be at.

(Organic solvent)

It is preferable that a pigment dispersion liquid contains the organic solvent.

An organic solvent is selected by the solubility of each component contained in a pigment dispersion liquid, and the applicability | paintability at the time of applying the pigment dispersion liquid to a coloring radiation sensitive composition. As an organic solvent which can be used for a pigment dispersion liquid, what is mentioned later as (E) organic solvent is mentioned.

As content of the organic solvent in a pigment dispersion, 50-95 mass% is preferable, and 70-90 mass% is more preferable.

(Polymer material)

In addition to the above-mentioned components, the pigment dispersion contains a polymer material having a structure other than that of the specific resin (B) from the viewpoints of improvement in dispersion stability and development control when the pigment dispersion is applied to a colored radiation-sensitive composition. It may further contain.

Examples of the polymer material having a structure other than that of the specific resin include polyamideamine and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth) acryl. And a (meth) acrylic copolymer (in particular, a (meth) acrylic acid copolymer containing a polymerizable group in the carboxylic acid group and the side chain is preferable), a naphthalene sulfonic acid formalin condensate, and the like. Since such a polymer material is adsorbed on the surface of the pigment and acts to prevent reagglomeration, terminal modified polymers, graft-type polymers, and block-type polymers having anchor sites to the pigment surface are preferable, for example, containing heterocycles. And graft copolymers containing a monomer and a polymerizable oligomer having an ethylenically unsaturated bond as a copolymer unit.

Examples of the polymer material having a structure other than that include polyamideamine phosphate, high molecular weight unsaturated polycarboxylic acid, polyether ester, aromatic sulfonic acid formalin polycondensate, polyoxyethylene nonylphenyl ether, polyesteramine, and polyoxyethylene sorbitan monooleate poly And oxyethylene monostearate.

The polymeric material of structures other than these may be used independently, and may be used in combination of 2 or more type.

As content of the polymeric material of the structure other than 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 further more preferable.

<Acrylic resin having partial structure represented by (B) 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).

R in formula (I) represents a hydrogen atom or a monovalent substituent. * Represents the site | part of the bond with the main chain structure of an acrylic resin.

Specific resin may have a partial structure represented by Formula (I), may superpose | polymerize the acrylic monomer which has a partial structure represented by Formula (I) independently, and has a partial structure represented by Formula (I) The acrylic resin obtained by copolymerizing a polymerizable unsaturated compound and another acrylic monomer may be sufficient. Moreover, the acrylic resin which couple | bonded the reactive compound which has the partial structure represented by Formula (I) to the side chain by polymer reaction with the acrylic resin may be sufficient.

Examples of the unsaturated compound having a partial structure represented by formula (I) include compounds in which an unsaturated group such as a vinyl group, a (meth) acryloyloxy group, or a (meth) acryl group is bonded to a * part of the formula (I) directly or through a linking group. Can be mentioned.

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. As a preferable coupling group, a single bond, a methylene group, an ethylene group, a propylene group, a phenylene group, etc. are mentioned.

Moreover, as an example of the unsaturated compound which has a partial structure represented by Formula (I), vinylureylene benzoimidazole, allylureylene benzoimidazole (meth) acryloyloxyureylene benzoimidazole, (meth) acryloyloxy Methylureylene benzoimidazole, (meth) acryloyloxyethylureylenebenzoimidazole, (meth) acryloyloxyphenylureylenebenzoimidazole and the like.

Among these, Preferably it is (meth) acryloyloxyethylureylene benzoimidazole.

As an acryl monomer which has a partial structure represented by Formula (I), the compound which has a (meth) acryloyloxy group as an unsaturated group among the unsaturated compounds which have a partial structure represented by said Formula (I) is mentioned.

Specific resin of this invention may further contain copolymerization components other than the unsaturated compound which has a partial structure represented by Formula (I), and it describes below.

As a copolymerization component other than the unsaturated compound which has a partial structure represented by Formula (I) which the specific resin of this invention may contain, for example, unsaturated which has at least 1 group chosen from the group which consists of an active methylene group and an active methine group Compound.

As an unsaturated compound which has at least 1 sort (s) of group chosen from the group which consists of an active methylene group and an active methine group, it is a compound represented by following formula (B-1) and formula (B-2).

(In formula (B-1) and (B-2), R <^1> represents the C1-C24 hydrocarbon group which may contain a hydrogen atom or a hetero atom. R <^2> represents a single bond or a C1-C20 divalent hydrocarbon group. R ³ represents a divalent group represented by any one of the following formulas (1-1) to (1-3): R ⁴ represents a group represented by any one of the following formulas (1-4) to (1-7): X represents a divalent group represented by any one 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 and the following formula (1) It is group represented by -11)-(1-13), More preferably, it is a hydrogen atom and 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, a dodecylene group, and more preferably a single bond, methylene Group, an ethylene group.

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

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

Compounds (I-1) to (I-7), (I-16), (II-1), (II-2) and (II-5) are compounds which induce structural units consisting of methacryl groups but are acryl groups The compound which guide | induces the structural unit which consists of is also mentioned.

Especially, 2- (methacryloyloxy) ethyl acetoacetate (compound represented by following (B-3)) is preferable.

Solvent resistance and developability become favorable when the specific resin of this invention contains the repeating unit derived from the unsaturated compound which has at least 1 group selected from the group which consists of an active methylene group and an active methine group. Although the content of the 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 is not particularly limited, the total repeating unit contained in the specific resin of the present invention is 100 mol%. It is preferable to contain 5 mol% or more of repeating units represented by either of general formula (B-1) and (B-2) to-, and it is more preferable to contain 10 mol%-40 mol%.

At least 1 type of repeating unit chosen from following formula (B-4) and (B-5) as copolymerization components other than the unsaturated compound which has the partial structure represented by Formula (I) which the specific resin of this invention may contain. More can be mentioned.

In the 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 each independently represent a single bond or a divalent organic linking group, and A ¹ and A ² each independently Monovalent organic group is represented, m and n respectively independently represent the integer of 2-8, p and q respectively independently represent the integer of 1-100.

As the monovalent organic group of R ¹ to R ⁶ , 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, A C1-C4 alkyl group is especially preferable.

When the alkyl group has a substituent, for example, as the substituent, a hydroxy group, an alkoxy group (preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), methoxy group, ethoxy group, cyclohexyloxy group Etc. can be mentioned. Specifically as a preferable alkyl group, For example, a methyl group, an ethyl group, a propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, a cyclohexyl group, 2-hydroxyethyl group, 3-hydroxy A propyl group, 2-hydroxypropyl group, and 2-methoxyethyl group are mentioned.

As R ¹ , R ² , R ⁴ and R ^{5, a} hydrogen atom is preferable, and as R ³ and R ⁶ , a hydrogen atom or a methyl group is most preferable from the point of adsorption efficiency on the pigment surface.

X ¹ and X ² are preferably -C (= 0) O-, -CONH-, or a phenylene group from the viewpoint of adsorption to the pigment, and -C (= 0) O- is most preferred.

As a divalent organic coupling group of L <^1> and L <^2> , a bivalent organic coupling group which consists of a substituted or unsubstituted alkylene group and the partial structure containing the said alkylene group and a hetero atom or a hetero atom is preferable. Here, as an alkylene group, a C1-C12 alkylene group is preferable, A C1-C8 alkylene group is more preferable, A C1-C4 alkylene group is especially preferable. Moreover, as a hetero atom in the partial structure containing a hetero atom, an oxygen atom, a nitrogen atom, and a sulfur atom are mentioned, for example, Especially, an oxygen atom and a nitrogen atom are preferable.

Specifically as a preferable alkylene group, a methylene group, an ethylene group, a propylene group, trimethylene group, tetramethylene group is mentioned, for example.

When an alkylene group has a substituent, a hydroxyl group etc. are mentioned as said substituent, for example.

As a divalent organic coupling group, it has a partial structure containing the hetero atom or hetero atom selected from -C (= O)-, -OC (= O)-, -NHC (= O)-at the terminal of the said alkylene group, It is preferable from the point of adsorption to a pigment that it connected with the adjacent oxygen atom through the said hetero atom or the partial structure containing a hetero atom. An adjacent oxygen atom means here the oxygen atom couple | bonded with L <^{1> in} general formula (B-4) and L <^2> in general formula (B-5) at a side chain terminal side.

As monovalent organic group of A <^1> and A <^2> , a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is preferable.

Examples of the preferred alkyl group include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups. , Nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, t-butyl, isopentyl, Neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group.

As the substituent of the substituted alkyl group, a group of monovalent nonmetallic atom groups except hydrogen is used, and as a preferred example, a halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkyl Thio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-aryl Amino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N -Alkyl-N-arylcarbamoyloxy group, alkyl sulfoxy group, aryl sulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylurea Pottery, N ', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylurei group 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-alkyl Ureido group, N ', N'-diaryl-N-arylureido 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, alkylsulphate Group, an aryl sulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-SO ₃ H) and (hereinafter referred to as sulfonate group), the salt conjugated device, an alkoxy sulfonyl group, aryloxy procedure Four group, sulfinyl cinnamoyl group, N-alkyl sulfinamoyl group, N, N-dialkyl sulfinamoyl group, N-aryl sulfinamoyl group, N, N- diaryl sulfinamoyl group, N-alkyl-N-aryl sulfinamoyl group, sulfamoyl group, N -Alkylsulfamoyl 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 phosphonate group), dialkylphosphono group (-PO ₃ (alkyl) ₂ ), diarylphosphono group (-PO ₃ (aryl) ₂ ), alkylaryl Phosphono group (-PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonate group), monoaryl phosphono group (-PO ₃ H (aryl)) and its conjugated salts device (hereinafter aryl phosphine pone Referred to as dawn), phosphono oxy group (-OPO ₃ H ₂₎ and its conjugated salts device (hereinafter referred to as phosphonium carbonate group), dialkyl phosphono oxy group _{(-OPO 3 (alkyl) 2)} , diaryl Phosphonooxy group (-OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (-OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (-OPO ₃ H (alkyl)) and its conjugate Base group (hereinafter referred to as alkylphosphonateoxy group), monoarylphosphonooxy group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as arylphosphonateoxy group), cyano group, nitro A group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, a silyl group is mentioned. 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, alkenyl group, alkynyl group, and silyl group are preferable from the point of dispersion stability.

Specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group and phenoxy Cyphenyl 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, sulfonatephenyl group, phosphonophenyl group, phosphonatephenyl group and the like.

As A <^1> and A <^2> , C1-C20 linear, C3-C20 branched, and C5-C20 cyclic alkyl group is preferable from dispersion stability and developability, and carbon atom number is preferable. 4-15 linear, 4-15 branched, and 6-10 carbon atoms are more preferred, and 6-10 carbon atoms, 6-12 carbon atoms. More preferred are branched alkyl groups.

m and n respectively independently represent the integer of 2-8. 4-6 are preferable and 5 is the most preferable from a dispersion stability and developability point.

p and q respectively independently represent the integer of 1-100. The other of p and the other of q may be mixed 2 or more types. 5-60 are preferable from a dispersion stability and developability point, 5-40 are more preferable, and, as for p and q, 5-20 are more preferable.

As specific resin in this invention, it is preferable to include the repeating unit represented with the said general formula (B-4) from the point of dispersion stability.

Moreover, as a repeating unit represented by Formula (B-4), it is more preferable that it is a repeating unit represented by following formula (B-6).

R <^1> -R <^3> respectively independently represents a hydrogen atom or monovalent organic group in said Formula (B-6), La represents a C2-C10 alkylene group, Lb is -C (= O)-or -NHC (= O)-, A <^1> represents monovalent organic group, m represents the integer of 2-8, p represents the integer of 1-100.

The repeating unit represented by formula (B-1), (B-2) or (B-6) polymerizes the monomer represented by the following formula (B-7), (B-8) or (B-9), respectively. Or it introduces as a repeating unit of specific resin by copolymerizing.

R <^1> -R <^6> respectively independently represents a hydrogen atom or monovalent organic group in said Formula (B-7)-(B-9), X <^1> and X <^2> respectively independently represent -CO- and -C (= O ) O-, -CONH-, -OC (= O)-, or a phenylene group, L ¹ and L ² each independently represent a single bond or a divalent organic linking group, and La represents an alkylene having 2 to 10 carbon atoms Represents a group, Lb represents -C (= 0)-or -NHC (= 0)-, A ¹ and A ² each independently represent a monovalent organic group, and m and n each independently represent an integer of 2 to 8; And p and q respectively independently represent the integer of 1-100.

Although the preferable specific example [monomer (A-1)-(A-23)] of the monomer represented by Formula (B-7)-(B-9) below is given to the following, this invention is not limited to these.

The content of the repeating unit represented by any one of formulas (B-4) and (B-5) is not particularly limited, but when the total repeating units contained in the specific resin of the present invention is 100 mol%, the formula (B-4) It is preferable to contain 30 mol% or more of repeating units represented by any one of () and (B-5), It is more preferable to contain 40 mol%, It is further more preferable to contain 50 mol%-70 mol%.

Moreover, it is an acidic group from the viewpoint of alkali developability, In particular, the monomer which has carboxyl groups, such as (meth) acrylic acid and itaconic acid, the monomer which has phenolic hydroxyl groups, such as N-hydroxyphenyl maleimide, maleic anhydride, itaconic anhydride, etc. It is preferable to include the monomer which has a carboxylic anhydride group as a copolymerization component.

Among these, it is preferable to contain (meth) acrylic acid as a copolymerization component. When content of an acidic group makes 100 mol% of all the repeating units contained in specific resin of this invention, it is preferable to contain 5 mol% or more, and it is more preferable to contain 10 mol%-30 mol%.

It is preferable to include aryl (meth) acrylate, alkyl (meth) acrylate, and polyethyleneoxy (meth) acrylate as copolymerization components which give usefulness from the viewpoint of ease of handling such as solubility in other organic solvents.

It is preferable to contain aryl (meth) acrylate or alkyl (meth) acrylate as a copolymerization component among these.

As aryl (meth) acrylate, benzyl methacrylate is mentioned, for example.

As alkyl (meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, for example , Acrylic acid esters and methacrylic acid esters having aliphatic hydroxyl groups such as 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, methyl acrylate, ethyl acrylate, acrylic acid Propyl, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate , Vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate Alkyl acrylates such as meth, propargyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, meta 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate , 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, propargyl methacrylate, and the like.

In addition, adding a compound having a radically polymerizable double bond to an unsaturated compound having a partial structure represented by the above formula (I) and a copolymer component other than the compound has a radiation-sensitive group in a specific resin. Since it is possible, it is a more preferable form.

Although the method of the process of adding the compound which has a radically polymerizable double bond depends on the kind of monomer which can add the compound which has a radically polymerizable double bond, For example, the monomer which has a carboxyl group, such as (meth) acrylic acid and itaconic acid, is added. When using, radical polymerization of epoxy groups, such as glycidyl (meth) acrylate, 3, 4- epoxycyclohexylmethyl (meth) acrylate, and o- (or m- or p-) vinylbenzyl glycidyl ether What is necessary is just to add the compound which has a sex double bond, and when using the monomer which has carboxylic acid anhydride groups, such as maleic anhydride and itaconic anhydride, hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, and radical polymerization What is necessary is just to add the compound which has a sex double bond, glycidyl (meth) acrylate, 3, 4- epoxycyclohexylmethyl (meth) acrylate, o- ( Alternatively, when a monomer having an epoxy group such as m- or p-) vinylbenzyl glycidyl 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 containing a radiation sensitive group in specific resin, 20-40 mol% is preferable as content of the copolymerization component which has a radiation sensitive group in the composition ratio in specific resin. By setting it as this range, since the hardenability of a radiation sensitive composition becomes high, linearity improvement and reduction of a residue can be aimed at further.

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

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

As content of the copolymerization component containing an 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, alkali developability of a colored radiation-sensitive composition improves and pattern formation property becomes especially favorable.

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

5000-30000 are preferable at a weight average molecular weight, as for the molecular weight of specific resin, 8000-25000 are more preferable, and 9000-20000 are the most preferable. By setting it as this range, the solubility in solvent and developability become favorable.

The weight average molecular weight is a value measured by gel permeation chromatography (GPC) and computed in polystyrene conversion here. GPC was measured using HLC-8020GPC (manufactured by Tosoh Corporation) and the column as TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ200 (manufactured by Tosoh Corporation).

Specific resin can be synthesize | combined according to the method of Unexamined-Japanese-Patent No. 2010-053307.

Although 1 type of specific resin should just be included in the colored radiation-sensitive composition of this invention, you may contain 2 or more types.

Moreover, what is necessary is just to include specific resin in a colored radiation-sensitive composition, and although you may add in any process of preparation of a colored radiation-sensitive composition, it is preferable to add in the preparation of a colored radiation-sensitive composition.

As for content of specific resin in the colored radiation-sensitive composition of this invention, 1-10 mass% is preferable with respect to the total solid of a colored radiation-sensitive composition, 2-8 mass% is more preferable, 2-6 mass% Is particularly preferred. By setting it in this range, the effect of this invention is fully exhibited.

In order to improve the S / N ratio of the solid-state imaging device, the colored pattern is a thin layer, but when the content of the colorant in the solid content of the colored radiation-sensitive composition is increased in order to realize the thin layer, a resin or a polymerizable compound which is a component other than the colorant in the solid content Component ratios, such as these fall. However, by using the specific resin (B), the alkali dissolution rate difference (discrimination) in the exposed and unexposed portions becomes larger than before, so that the unexposed portions exhibit high developability, the linearity of the pattern is improved, and the residue can be reduced. . Therefore, even when there is much content of a coloring agent, the coloring pattern of an exposure part becomes a rectangle, and the residue of the periphery of a pixel can be reduced, and surface roughness suppression and exposure dose dependence (thickness | thickness thickness) of a coloring pattern can also be suppressed. Thereby, refinement | miniaturization of a coloring pattern is attained.

&Lt; (C) Polymerizable compound >

The radiation sensitive composition of this invention contains the (C) polymeric compound.

The polymerizable compound (C) is specifically selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Especially, the tetrafunctional or more than polyfunctional polymerizable compound is preferable, and 5-functional or more is more preferable.

Such compound groups are widely known in the above industrial fields, and in the present invention, these can be used without particular limitation. These may be any of chemical forms 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 the monomer and its prepolymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and the like. Multimers are mentioned, Preferably they are ester of unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and amides of unsaturated carboxylic acid and an aliphatic polyamine compound, and these multimers. Furthermore, the addition reaction, monofunctional or polyfunctional carboxylic acid of unsaturated carboxylic acid ester or amide which has nucleophilic substituent, such as a hydroxyl group, an amino group, and a mercapto group, and monofunctional or polyfunctional isocyanate, or epoxy, Dehydration condensation reactants and the like are also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, and desorption substituents such as halogen groups and tosyloxy groups Substituted reactants of unsaturated carboxylic acid esters or amides with monofunctional or polyfunctional alcohols, amines and thiols are also preferable. As another example, a compound group substituted with a vinylbenzene derivative such as unsaturated phosphonic acid and styrene, vinyl ether, allyl ether, or the like may be used instead of the above unsaturated carboxylic acid.

As these specific compounds, the compound described in Paragraph No. [0095]-[0108] of Unexamined-Japanese-Patent No. 2009-288705 can also be used suitably also in this invention.

Moreover, as said polymeric compound, the compound which has an ethylenically unsaturated group which has an ethylenic group which can carry out at least 1 addition polymerization and has a boiling point of 100 degreeC or more under normal pressure is also preferable. Examples thereof 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, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tree ( (Meth) acrylated after adding ethylene oxide or propylene oxide to polyfunctional alcohols such as acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylol ethane, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Publication No. 51-37193 Urethane (meth) acrylates, polyester acrylates and epoxy resins described in Japanese Patent Application Laid-open No. 48-64183, Japanese Patent Publication No. 49-43191 and Japanese Patent Publication No. 52-30490; Polyfunctional acrylates and methacrylates such as epoxy (meth) acrylates which are reaction products of (meth) acrylic acid; And mixtures thereof.

The polyfunctional (meth) acrylate etc. which are obtained by making the compound which has cyclic ether groups, such as glycidyl (meth) acrylate, and ethylenically unsaturated group react to polyfunctional carboxylic acid are mentioned.

Moreover, the compound which has a fluorene ring as described in Unexamined-Japanese-Patent No. 2010-160418, each Unexamined-Japanese-Patent No. 2010-129825, the specification of Unexamined-Japanese-Patent No. 4364216, etc., and has an ethylenically unsaturated group bifunctional or more, Cardo resin can also be used.

Moreover, the compound of Paragraph No. [0254]-[0257] of Unexamined-Japanese-Patent No. 2008-292970 is also preferable as a compound which has a boiling point of 100 degreeC or more under normal pressure, and has at least 1 addition-polymerizable ethylenically unsaturated group.

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

In said general formula, n is 0-14, m is 1-8. Two or more R and T in one molecule may be same or different, respectively.

The formula (MO-1) ~ (MO -5) at least one of the plurality of R exist in each of the polymerizable compound is more -OC (= O) CH = CH ₂ or -OC (= O) represented by the The group represented by C (CH ₃ ) = CH ₂ is shown.

As a specific example of the polymeric compound represented by said general formula (MO-1)-(MO-5), Paragraph No. 0248 of Unexamined-Japanese-Patent No. 2007-269779-paragraph No. 0251 are also preferable in this invention. Can be used.

In addition, after adding ethylene oxide or propylene oxide to the above-mentioned polyfunctional alcohol as described in the general formulas (1) and (2) in Japanese Patent Application Laid-open No. Hei 10-62986 and the specific examples thereof, (meth) acrylated The compound can also be used as the polymerizable compound.

Especially, as a polymeric compound, dipentaerythritol triacrylate (as a commercial item, KAYARAD D-330; made by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial item, KAYARAD D-320; Nippon Kayaku Co., Ltd. make) ), Dipentaerythritol penta (meth) acrylate (as a commercially available product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as commercially available products, KAYARAD DPHA; Nippon Kayaku Co., Ltd.) ), And the structure of Nippon Kayaku Co., Ltd. A-DPH-12E and these (meth) acryloyl groups via ethylene glycol and a propylene glycol residue are preferable. These oligomer types can also be used. The form of a preferable polymeric compound is shown below.

As a polymerizable compound, you may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group, as a polyfunctional monomer. As long as the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, it can be used as it is, but if necessary, a non-aromatic carboxylic anhydride is reacted with the hydroxyl group of the ethylenic compound to introduce an acid group. You may also Specific examples of the non-aromatic carboxylic anhydride used in this case include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the non-reactive hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to give an acid group. A functional monomer is preferable, and aliphatic polyhydroxy compound is especially preferably pentaerythritol and / or dipentaerythritol in this ester. As a commercial item, M-510, M-520, etc. are mentioned as a Toagosei Co., Ltd. polybasic acid modified | denatured acrylic oligomer, for example.

Although the 1 type of these polymeric compounds may be used independently for the colored radiation-sensitive composition of this invention, since it is difficult to obtain a single compound in manufacture of a polymeric compound, you may mix and use 2 or more types.

Moreover, you may use together the polyfunctional monomer which does not have an acidic radical, and the polyfunctional monomer which has an acidic radical as a polymeric compound as needed.

As a preferable acid value of the polyfunctional monomer which has an acidic radical, it is 0.1-40 mgKOH / g, Especially preferably, it is 5-30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are poor. If the acid value of the polyfunctional monomer is too high, manufacturing and handling are difficult, and the photopolymerization performance is poor, resulting in inferior sclerosis such as surface smoothness of the pixel. Therefore, when using 2 or more types of polyfunctional monomers of another acidic group together, or when using together with the polyfunctional monomer which does not have an acidic radical, it is preferable to adjust so that the acidic radical as the whole polyfunctional monomer may fall in the said range.

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 its molecule, but for example, trimethylol ethane, ditrimethylol ethane, trimethylol propane, ditrimethylol propane, pentaerythritol, dipenta Ε-caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as erythritol, tripentaerythritol, glycerin, diglycerol, trimethylol melamine, and (meth) acrylic acid and ε-caprolactone. . Especially, the polyfunctional monomer which has a caprolactone structure represented by the following general formula (Z-1) is preferable.

Six R in general formula (Z-1) are group represented by the following general formula (Z-2), or 1-5 of 6 R are group represented by the following general formula (Z-2), The residual is a group represented by the following general formula (Z-3).

R <^1> represents a hydrogen atom or a methyl group in general formula (Z-2), m shows the number of 1 or 2, and it shows that "*" is a bond.

(In general formula (Z-3), R <^1> represents a hydrogen atom or a methyl group, and "*" represents a bond.)

The polyfunctional monomer which has such a caprolactone modified structure is commercially available from Nippon Kayaku Co., Ltd. as a KAYARAD DPCA series, for example, and DPCA-20 (m = 1, Formula (1) in said Formula (1)-(3). The number of groups represented by 2) = 2, the compound in which R <^1> is all hydrogen atoms), DPCA-30 (The number of groups represented by the formula, m = 1, Formula (2) = 3, R <^1> are all hydrogen. A compound that is an atom), DPCA-60 (the compound represented by the formula, m = 1, the number of groups represented by the formula (2) = 6, R ¹ are all hydrogen atoms), DPCA-120 (m = 2 in the formula) , The number of groups represented by Formula (2) = 6, the compound whose R <^1> is all hydrogen atoms, etc. are mentioned.

In this invention, the polyfunctional monomer which has a caprolactone modified structure can be used individually or in mixture of 2 or more types.

As the polymerizable compound in the present invention, a polymerizable compound containing an alkyleneoxy group having 2 or more carbon atoms (ethyleneoxy group, propyleneoxy group, butyleneoxy group, etc.) is preferable.

It is especially preferable that it is at least 1 sort (s) chosen from the group of the compound represented by the following general formula (i) or (ii) among the polymeric compound containing a C2 or more alkyleneoxy group.

In formulas (iii) and (ii), E each independently represents-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-, and y is each independently The integer of 0-10 is shown, and X represents acryloyl group, methacryloyl group, a hydrogen atom, or a carboxyl group each independently.

The sum of the acryloyl group and the methacryloyl group represented by X in general formula (i) is three or four, m respectively independently represents the integer of 0-10, and the sum of each m is 0-40 Is an integer. However, when the sum of each m is 0, any one of X is a carboxyl group.

In general formula (ii), the sum of the acryloyl group and the methacryloyl group represented by X is five or six, n respectively independently represents the integer of 0-10, and the sum of each n is 0-60 Is an integer. However, when the sum of each n is 0, any one of X is a carboxyl group.

In general formula (i), the integer of 0-6 is preferable and, as for m, the integer of 0-4 is more preferable. Moreover, the integer of 2-40 is preferable, as for the sum total of each m, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable.

In general formula (ii), the integer of 0-6 is preferable and, as for n, the integer of 0-4 is more preferable. Moreover, the integer of 3-60 is preferable, the integer of 3-24 is more preferable, and, as for the sum total of each n, the integer of 6-12 is especially preferable.

- ((CH ₂ ) _y CH ₂ O) - or - ((CH ₂ ) _y CH (CH ₃ ) O) - in the general formula (i) or (ii) Is preferable.

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, the form in which all six X's in general formula (ii) are acryloyl group is preferable.

Compounds represented by the general formula (i) or (ii) include a step of binding an opening ring skeleton by ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known step, and a terminal hydroxyl group of the ring-opening skeleton. For example, it can synthesize | combine from the process of reacting (meth) acryloyl chloride and introducing a (meth) acryloyl group. Each process is a well-known process, and a person skilled in the art can easily synthesize | combine the compound represented by general formula (i) or (ii).

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

In particular, the polymerizable compound which has an ethyleneoxy group and 5 or more (meth) acryloyl groups in a molecule | numerator is preferable. As a total number of ethyleneoxy groups contained in a molecule | numerator, 2-10 pieces are preferable and 4-8 pieces are more preferable.

By containing a polymerizable compound having an ethyleneoxy group and five or more (meth) acryloyl groups in a colored radiation-sensitive composition in a molecule, the solubility in an alkali developer of the non-exposed part is improved, resulting in demineralization of the exposed and non-exposed parts. Since it becomes easy, the linearity of a coloring pattern improves and reduction of the residue other than a coloring pattern area can be aimed at.

Specifically, the compound (henceforth "exemplified compound (a)-(f)") represented by following formula (a)-(f) is mentioned, Especially, exemplary compound (a)-(d) is preferable. And the effect of this invention can be improved significantly.

As a commercial item of the polymeric compound represented by General formula (i) and (ii), SR-494 which is a tetrafunctional acrylate which has four ethyleneoxy chains made by Satomer, and a pen made by Nippon Kayaku Co., Ltd. DPCA-60 which is a 6 functional acrylate which has 6 thylene oxy chains, TPA-330 which is a trifunctional acrylate which has 3 isobutylene oxy chains, etc. are mentioned.

Moreover, you may mix | blend the polymeric compound of the other structure which has two or more polymeric groups with the polymeric compound used for this invention to the colored radiation-sensitive composition of this invention.

As said "polymerizable compound of the other structure which has two or more polymerizable functional groups", for example, polyethyleneglycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, 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 (Meth) acrylated after adding ethylene oxide or propylene oxide to polyfunctional alcohols such as (acryloyloxyethyl) isocyanurate, glycerin and trimethylol ethane, Japanese Patent Publication No. 48-41708, Urethane acrylates described in Japanese Patent Application Publication No. 50-6034, Japanese Patent Application Publication No. 51-37193, etc. The polyester acrylates described in each publication, such as Unexamined-Japanese-Patent No. 48-64183, Unexamined-Japanese-Patent No. 49-43191, and 52-30490, Epoxy which is a reaction product of an epoxy resin and (meth) acrylic acid Polyfunctional acrylates and methacrylates, such as acrylates, are mentioned.

Moreover, the thing introduce | transduced as a photocurable monomer and oligomer can also be used by Japanese adhesive association Vol.20, No.7 (pages 300-308).

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

<(D) UV absorber>

The colored radiation-sensitive composition of the present invention contains a ultraviolet absorber.

[UV absorber]

As a ultraviolet absorber, the compound represented by the following general formula (II) which is a conjugated diene type compound is especially preferable.

In 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 simultaneously represent a hydrogen atom There is no work. Or R ¹ and R ² together with the nitrogen atom to which R ¹ and R ² bind form a cyclic amino group. R ³ and R ⁴ each independently represent a monovalent group. Or R ³ and R ⁴ combine with each other to form a ring.

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, a halogen atom, an acylamino group, an acyl group, and an alkyl tea. Or arylthio group, hydroxy group, cyano group, alkyloxycarbonyl group, aryloxycarbonyl group, substituted carbamoyl group, substituted sulfamoyl group, nitro group, substituted amino group, heterocyclic group, alkylsulfonyl group, arylsulfonyl group, etc. may be mentioned. .

The alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² is, for example, a methyl group, ethyl group, propyl group, n-butyl group, n-hexyl group, cyclohexyl group, 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, 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, etc. are mentioned, A methyl group, an ethyl group, a propyl group, n-butyl group, n-hexyl group is preferable.

The aryl group having 6 to 20 carbon atoms represented by R ¹ and R ² may be monocyclic or condensed, or any of a substituted aryl group and an unsubstituted aryl group having a substituent may be used. For example, a phenyl group, 1-naphthyl group, 2-naphthyl group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group, fluorenyl group, etc. are mentioned. As a substituent of the substituted aryl group which has a substituent, 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 hydroxyl group, a cyano group, Alkyloxycarbonyl group, aryloxycarbonyl group, substituted carbamoyl group, substituted sulfamoyl group, nitro group, substituted amino group, alkylsulfonyl group, arylsulfonyl group, etc. are mentioned. Especially, a substituted or unsubstituted phenyl group, 1-naphthyl group, and 2-naphthyl group are preferable.

In addition, when R ¹ and R ² form a cyclic amino group together with the nitrogen atom to which they are bonded, the cyclic amino group is, for example, a piperidino group, a morpholino group, a pyrrolidino group, a hexahydroazino group, a piperazino group, or the like. Can be mentioned.

Among the above, R ¹ and R ² include lower alkyl groups having 1 to 8 carbon atoms (for example, methyl, ethyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, octyl, 2- Ethyl hexyl, tert-octyl and the like or a substituted or unsubstituted phenyl group (for example, a tolyl group, a phenyl group, an acyl group, a mesityl group, a chlorophenyl group, a 2,4-di-tert-amylphenyl group, etc.) is preferable. Moreover, it is also preferable that R <^1> and R <^2> combine and form the ring (for example, a piperidine ring, a pyrrolidine ring, a morpholine ring, etc.) containing the nitrogen atom represented by N in a formula.

In the general formula (II), the monovalent group represented by R ³ and R ⁴ is preferably an electron withdrawing group. Here, an electron withdrawing group is an electron withdrawing group whose Hammer substituent constant (sigma) _p value (henceforth simply "sigma _p value") is 0.20 or more and 1.0 or less. Preferably an electron withdrawing group in a range from a σ _p value of 0.30 to 0.8.

Hammetrul is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, but this has been widely accepted today. Substituent constants obtained by Hametrule have values of σ _p and σ _m , and these values are described in many common texts, but for example, JA Dean's Handbook of Chemistry, twelfth edition, 1979 (Mc Graw-Hill) or "Additional Chemistry," No. 122, pp. 96-103, 1979 (Namkang Hall), Chemical Reviews, 91, pp. 165-195, 1991. The present invention is not meant to be limited only to substituents having known values described in these texts, but the value is of course included even if the value is unknown, as long as it is included in the range when measured based on Hammet's rule.

Specific examples of electron withdrawing groups having σ _p values of 0.20 or more and 1.0 or less include acyl, acyloxy, carbamoyl, alkyloxycarbonyl, aryloxycarbonyl, cyano, nitro, dialkylphosphono and diarylphosphono Group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, at least two halogen atoms A substituted alkyl group, an alkoxy group substituted with at least two halogen atoms, an aryloxy group substituted with at least two halogen atoms, an alkylamino group substituted with at least two halogen atoms, an alkylthio group substituted with at least two halogen atoms, σ _p value, an aryl group substituted with another electron withdrawing group of 0.20 or more, a heterocyclic group, a chlorine atom, a bromine atom, an azo group or a seleno cyanate group The can. The group which can further have a substituent among these substituents may further have a substituent listed above.

Among these, as R ³ and R ⁴ , acyl group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group and sulfamoyl group are particularly preferable. Preferred are a real 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.

Among the above, in the present invention, R ³ is preferably a cyano group, -COOR ⁵ , -CONHR ⁵ , -COR ⁵ , -SO ₂ R ⁵ , and as R ⁴ , a cyano group, -COOR ⁶ , -CONHR ⁶ Groups selected from -COR ⁶ and -SO ₂ R ⁶ are preferred. R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The C1-C20 alkyl group and C6-C20 aryl group represented by R <^5> and R <^6> are synonymous with the case in said R <^1> and R <^2> , and its preferable aspect is also the same.

R ³ and R ⁴ may be bonded to each other to form a ring (for example, a saturated or unsaturated 6-membered ring or the like).

At least one of 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. The copolymer with another monomer may be sufficient. In the case of the copolymer, other monomers include esters derived from acrylic acids such as acrylic acid, α-chloroacrylic acid and α-arylacrylic acid (e.g., methacrylic acid, preferably lower alkyl esters and amides such as acrylamide, meta). Acrylamide, t-butylacrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acryl Acrylate, octyl methacrylate and lauryl methacrylate, methylenebisacrylamide, etc., vinyl esters (e.g., vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, Aromatic vinyl compounds (e.g. styrene and derivatives thereof, e.g. vinyltoluene, divinylbenzene, vinylacetate) Phenone, sulfostyrene and styrenesulfonic acid, etc.), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g., vinyl ethyl ether, etc.), maleic acid esters, N-vinyl-2-pi Rollidone, N-vinylpyridine, 2- and 4-vinylpyridine and the like.

Among these, acrylic acid esters, methacrylic acid esters and aromatic vinyl compounds are preferable.

You may use together 2 or more types of said other monomer compounds together. For example, n-butyl acrylate, divinylbenzene, styrene, methyl methacrylate, methyl methacrylate, methacrylic acid, etc. can be used together.

Hereinafter, the preferable specific example [example compound (1)-(14)] of the compound represented by the said general formula (II) is shown. However, the present invention is not limited thereto.

The ultraviolet absorber represented by the general formula (II) is Japanese Patent Publication No. 44-29620, Japanese Patent Publication No. 53-128333, Japanese Patent Publication No. 61-169831, Japanese Patent Publication No. 63-53543, Japanese Patent Publication No. 63 -53544, Japanese Patent Laid-Open No. 63-56651, and the like, and the method described in the pamphlet of WO 2009/123109. Specifically, the exemplary compound (1) can be synthesized by the method described in WO 2009/123109 pamphlet paragraph number 0040.

As the ultraviolet absorber, ultraviolet absorbers such as salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine can be used.

Examples of the salicylate ultraviolet absorber include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and the like, and examples of the benzophenone ultraviolet absorber include 2,2'-dihydroxy-. 4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-meth Oxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and the like. In addition, examples of the benzotriazole-based ultraviolet absorber include 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 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) benzotriazole, 2- [2'-hydroxy-5 '-(1,1,3,3-tetramethyl) phenyl] benzotriazole, etc. are mentioned.

As an example of a substituted acrylonitrile-type ultraviolet absorber, 2-cyano-3, 3- diphenyl acrylate ethyl, 2-cyano-3, 3- diphenyl acrylate 2-ethylhexyl, etc. are mentioned. In addition, 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-dimethyl Mono, such as phenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine (Hydroxyphenyl) triazine compounds; 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-hydrate Hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropyloxy) phenyl] -1 Tris (hydroxyphenyl) triazine compounds, such as a 3, 5- triazine, etc. are mentioned.

In this invention, the said various ultraviolet absorbers may be used individually by 1 type, and may be used in combination of 2 or more type.

As a preferable ultraviolet absorber, they are exemplary compounds (1)-(14), Especially preferably, they are exemplary 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 the ultraviolet absorber based on the solid content of the colored radiation-sensitive composition.

Moreover, as content of a preferable ultraviolet absorber, it is 0.5 mass%-6 mass% with respect to solid content of a colored radiation-sensitive composition, and 1 mass%-5 mass% are more preferable.

By setting it as this range, when the 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 outside the colored pattern region can be reduced.

<(E) Photoinitiator>

It is preferable that the colored radiation-sensitive composition of this invention contains the (E) photoinitiator.

As the (E) photopolymerization initiator (hereinafter, simply referred to as "polymerization initiator") in the present invention, those known as photopolymerization initiators described below can be used.

As a photoinitiator in this invention, as long as it has the ability to start superposition | polymerization of the said polymeric compound, it can select from a well-known photoinitiator suitably without limitation in particular. For example, it is preferable to have photosensitivity with respect to the light of a suitable wavelength range from an ultraviolet region to a visible region. Moreover, it may be an activator which generates an active radical by generating any action with a photoexcited sensitizer, or may be an initiator that initiates cationic polymerization depending on the type of monomer.

Moreover, it is preferable that the photoinitiator contains at least 1 sort (s) of the compound which has a molecular extinction coefficient of at least about 50 in the range of about 300 nm-800 nm (330 nm-500 nm are more preferable).

Examples of the (E) photopolymerization initiator in the present invention include acylphosphine compounds such as halogenated hydrocarbon derivatives (eg, those having a triazine skeleton, those having an oxadiazole skeleton), and acylphosphine oxide, Oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenone and the like.

As the halogenated hydrocarbon compound having the triazine skeleton or the oxadiazole skeleton, for example, compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in British Patent 1388492, J. Org. Chem. By the compound of Japanese Patent Laid-Open No. 53-133428, the compound of German Patent No. 3337024, FCSchaefer and the like; 29, 1527 (1964) compound, the compound of Unexamined-Japanese-Patent No. 62-58241, the compound of Unexamined-Japanese-Patent No. 5-281728, the compound of Unexamined-Japanese-Patent No. 5-34920, United States The compound described in patent 4212976 specification, etc. are mentioned.

As the compound described in the above-mentioned US Patent No. 4212976, for example, a compound having an oxadiazole skeleton (eg, 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-Chrolstyryl) -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- Tribromomethyl-5-styryl-1,3,4-oxadiazole etc.) etc. are mentioned.

Moreover, as a polymerization initiator of that excepting the above, an acridine derivative (for example, 9-phenylacridine, 1,7-bis (9,9'- acridinyl) heptane, etc.), glycine (for example, N-phenylglycine, etc.), polyhalogen compounds (e.g., carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (e.g., 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 ' -Carbonylbis (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- Zotriazole-2-ylcoumarin, also Japanese Patent Laid-Open No. 5-19475, Japanese Patent Laid-Open No. 7-271028, Japanese Patent Laid-Open No. 2002-363206, Japanese Patent Laid-Open No. 2002-363207, Japanese Patent Coumarin compounds disclosed in Japanese Unexamined Patent Publication No. 2002-363208, Japanese Unexamined Patent Application Publication No. 2002-363209, etc., acylphosphine oxides (for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis) (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, LucirinTPO, etc., metalocenes (for example, bis (η5-2,4-cyclopentadiene-1-) Yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), the compounds described in Japanese Patent Laid-Open No. 53-133428, Japanese Patent Laid-Open No. 57-1819, Japanese Patent Laid-Open No. 57-6096, and US Patent No. 3615455. The.

Examples of the ketone compounds listed as specific examples of the polymerization initiator include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4 -Chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or tetramethylester thereof, 4,4'-bis (dialkylamino) Benzophenones (eg, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bisdicyclohexylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4 , 4'-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoaceto Phenone, benzil, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthhraquinone, xanthone, thioxanthone, 2-croc-thioxanthone, 2,4-diethyl Oxanthone, 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 (e.g., benzoin methyl ether, benzoin ethyl ether) , Benzoin propylether, benzoin isopropyl ether, benzoin phenyl ether, benzyldimethyl ketal), acridon, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloro Acridon etc. are mentioned.

As a polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be used preferably. More specifically, for example, the aminoacetophenone initiators described in Japanese Patent Application Laid-open No. Hei 10-291969 and the acylphosphine oxide initiators described in Japanese Patent No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Corporation) can be used. As an aminoacetophenone type initiator, the compound of Unexamined-Japanese-Patent No. 2009-191179 which the absorption wavelength matched to longwave light sources, such as 365 nm or 405 nm, can also be used. Moreover, as an acyl phosphine type initiator, IRGACURE-819 and DAROCUR-TPO (all of brand names: BASF Corporation make) which are commercial items can be used.

More preferably, an oxime compound is mentioned as a polymerization initiator. As a specific example of an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-80068, and the compound of Unexamined-Japanese-Patent No. 2006-342166 can be used.

Examples of oxime compounds such as oxime derivatives which are preferably used as polymerization initiators in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one and 3-propionyloxyiminobutane-. 2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4- Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

Examples of oxime compounds are JCSPerkin II (1979) pp. 1653-1660), JCSPerkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, Japanese Patent Publication 2000 The compound of Unexamined-Japanese-Patent No. -66385, Unexamined-Japanese-Patent No. 2000-80068, Unexamined-Japanese-Patent No. 2004-534797, Unexamined-Japanese-Patent No. 2006-342166, etc. are mentioned.

As a commercial item, IRGACURE OXE-01 (made by BASF Corporation) and IRGACURE OXE-02 (made by BASF Corporation) are also used preferably.

In addition, the compound described in JP-A-2009-519904 in which an oxime is linked to the N-position of carbazole as an oxime compound other than the above, and the compound and pigment portion described in US Patent 7626957, wherein a heterosubstituent is introduced into the benzophenone moiety. Contain the compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, the ketooxime compound described in International Publication No. 2009-131189, the triazine skeleton and the oxime skeleton in the same molecule. You may use the compound of Unexamined-Japanese-Patent No. 7556910, the compound of Unexamined-Japanese-Patent No. 2009-221114 which has an absorption maximum at 405 nm, and has favorable sensitivity with respect to a g-ray light source.

Preferably, it can use more also about the cyclic oxime compound described in Unexamined-Japanese-Patent No. 2007-231000 and 2007-322744. Among the cyclic oxime compounds, the cyclic oxime compounds condensed with the carbazole dyes described in JP 2010-32985 A and JP 2010-185072 A are particularly preferable from the viewpoint of high sensitivity.

Moreover, the compound described in Unexamined-Japanese-Patent No. 2009-242469 which has an unsaturated bond in the specific site of an oxime compound can also achieve high sensitivity by regenerating an active radical from a polymerization inert radical, and can use it preferably.

Most preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-269779, and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.

Specifically, as an oxime compound, the compound represented by a following formula (OX-1) is preferable. The oxime N-O bond may be an oxime compound of (E) or an oxime compound of (Z) or a mixture of (E) and (Z).

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.

As a monovalent substituent represented by R in general formula (OX-1), it is preferable that it is a monovalent nonmetallic atom group.

Examples of the monovalent non-metallic 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. In addition, these groups may have one or more substituents. In addition, the substituent mentioned above may further be substituted by the other 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.

As an alkyl group which may have a substituent, a C1-C30 alkyl group is preferable, Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, an isopropyl group, Isobutyl group, sec-butyl group, t-butyl group, 1-ethyl pentyl 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-fluoro A phenacyl group, 3-trifluoromethyl phenacyl group, and 3-nitrophenacyl group can be illustrated.

As an aryl group which may have a substituent, a C6-C30 aryl group is preferable, Specifically, a phenyl group, a biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1- Pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl, 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, vinphthalenyl group, ternaphthalenyl group, quarternaphthalenyl group, heptalenyl group, biphenylenyl group, indasenyl group , Fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, penalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl Group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, pleadenyl group, pisenyl group, peryllenyl group, pentaphenyl group, pen Hexenyl group, a tetraphenyl group LES, there can be mentioned hexadecyl group, a hexadecyl hexenyl group, a hexenyl group ruby, nose Ro group, tri tilre naphthyl group, a heptadecyl group, a heptadecyl hexenyl group, a pyran group, and five trays ballet carbonyl group.

As an acyl group which may have a substituent, a C2-C20 acyl group is preferable, Specifically, an acetyl group, propanoyl group, butanoyl group, trifluoroacetyl group, pentanoyl group, benzoyl group, 1-naphthoyl group, 2 -Naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2- Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-sia A nobenzoyl group and 4-methoxybenzoyl group can be illustrated.

As an alkoxycarbonyl group which may have a substituent, a C2-C20 alkoxycarbonyl group is preferable, Specifically, a methoxycarbonyl group, an ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, An octadecyloxycarbonyl group and a trifluoromethyloxycarbonyl group can be illustrated.

Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, 4- Dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group , 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group and 4-methoxyphenyloxycarbonyl group can do.

As a heterocyclic group which may have a substituent, the aromatic or aliphatic heterocycle containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom is preferable.

Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxa Thiynyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolinyl group, isoindolinyl group, 3H-indolyl group , Indolyl group, 1H-indazolyl group, furinyl group, 4H-quinolinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnaolinyl group, Pterridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenantridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenarsazinyl group, Isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromenyl group, chromanyl group, pyrrolidinyl group, pyrroli Nyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinucridinyl group, morpholinyl group and tee Orcanthol tolyl group can be illustrated.

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

Specific examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, and 4-dimethylaminophenylthio. Carbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group, 3-tri Fluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group, and 4-methoxyphenylthiocarbonyl group.

As monovalent substituent represented by B in the said general formula (OX-1), an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group is represented. In addition, these groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified. In addition, the substituent mentioned above may further be substituted by the other substituent.

Among them, particularly preferred is the structure shown below.

In the following structure, Y, X, and n are synonymous with Y, X, and n in General formula (OX-2) mentioned later, and a preferable example is also the same.

As a bivalent organic group represented by A in general formula (OX-1), a C1-C12 alkylene group, a cycloalkylene group, and an alkynylene group is mentioned. In addition, these groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified. In addition, the substituent mentioned above may further be substituted by the other substituent.

Especially, as A in Formula (OX-1), since it improves a sensitivity and suppresses coloring by the time of heating, an unsubstituted alkylene group, an alkyl group (for example, methyl group, an ethyl group, tert- butyl group, dode) Alkylene group substituted by the actual group), Alkylene group substituted by the alkenyl group (for example, vinyl group, allyl group), Aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group) , An alkylene group substituted with an anthryl group, a phenanthryl group, or a styryl group) is preferable.

As an aryl group represented by Ar in general formula (OX-1), a C6-C30 aryl group is preferable and may have a substituent. As a substituent, the thing similar to the substituent introduce | transduced into the substituted aryl group mentioned as the specific example of the aryl group which may have a substituent can be illustrated.

Among them, a substituted or unsubstituted phenyl group is preferred in view of increasing the sensitivity and suppressing coloration due to heating and aging.

In general formula (OX-1), it is preferable from the point of a sensitivity that the structure of "SAr" formed from Ar in general formula (OX-1) and S adjacent to it is a structure shown below. Me represents a methyl group, and Et represents an ethyl group.

It is preferable that an oxime compound is a compound represented with 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 is an integer of 0 to 5).

R, A and Ar in Formula (OX-2) are synonymous with R, A and Ar in said Formula (OX-1), and its preferable example is also the same.

Examples of the monovalent substituent represented by X in General Formula (OX-2) include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic group, and a halogen atom. In addition, these groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified. In addition, the substituent mentioned above may be substituted by the other substituent.

Among these, as X in general formula (OX-2), an alkyl group is preferable at the point of solvent solubility and the absorption efficiency improvement of a long wavelength region.

In addition, n in Formula (OX-2) represents the integer of 0-5, and the integer of 0-2 is preferable.

Examples of the divalent organic group represented by Y in General Formula (OX-2) include the structures shown below. In addition, in the group shown below, "*" shows the coupling | bonding position with the carbon atom adjacent to Y in general formula (OX-2).

Especially as a photoinitiator, what has a structure shown below from a viewpoint of high sensitivity is preferable.

Moreover, it is preferable that an oxime compound is a compound represented with the following general formula (OX-3).

(In 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) are synonymous with R, X, A, Ar and n in general formula (OX-2), and a preferable example is also the same.

Although the specific example of the oxime compound used preferably below is shown below, this invention is not limited to these.

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

It is preferable that the molar extinction coefficient in 365 nm or 405 nm is 1,000-300,000 from a viewpoint of a sensitivity, It is more preferable that it is 2,000-300,000, It is especially preferable that it is 5,000-200,000.

Although the molar extinction coefficient of a compound can use a well-known method, Specifically, it is preferable to measure it by the ultraviolet visible spectrophotometer (Carry-5 spctrophotometer by Varian) at the density | concentration of 0.01 g / L using ethyl acetate solvent, for example. .

You may use the polymerization initiator used for this invention in combination of 2 or more type as needed.

As an (E) photoinitiator used for the colored radiation-sensitive composition of this invention, a trihalomethyl triazine compound, a benzyl dimethyl ketal compound, the (alpha)-hydroxy ketone compound, the (alpha)-amino ketone compound, an acyl phos from the viewpoint of exposure sensitivity. Fin compounds, phosphine oxide compounds, metalocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes And a salt, a halomethyloxadiazole compound, or a compound selected from the group consisting of a 3-aryl substituted coumarin compound.

More preferably, they are a trihalomethyl triazine compound, an α-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzophenone compound, an acetophenone compound, Most preferred is at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound.

In particular, when the colored radiation-sensitive composition of the present invention is used for the production of a color filter included in a solid-state imaging device, a fine pattern is formed in a sharp shape, and in order to improve the linearity of the colored pattern, the residue remains on the non-exposed portion together with curability. It is important to develop without. From such a viewpoint, it is especially preferable to use an oxime compound as a polymerization initiator. Particularly, when a fine pattern is formed in a solid-state imaging device, stepper exposure is used for curing exposure, but the exposure machine may be damaged by halogen, and the amount of addition of the polymerization initiator needs to be kept low, so these points are removed. In consideration of the above, it is most preferable to use an oxime compound as the (E) polymerization initiator in order to form the same fine pattern as the solid-state imaging device.

It is preferable that content of the (E) polymerization initiator contained in the colored radiation-sensitive composition of this invention is 0.1 mass% or more and 50 mass% or less with respect to the total solid of a colored radiation sensitive composition, More preferably, it is 0.5 mass% or more. It is mass% or less, More preferably, it is 1 mass% or more and 15 mass% or less. In this range, good sensitivity and pattern formability are obtained.

<(F) organic solvent>

The colored radiation-sensitive composition of the present invention contains an organic solvent.

As an example of an organic solvent, the following are mentioned, for example.

As esters, for example, ethyl acetate, acetic acid-n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, oxy Alkyl acetates (e.g. methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g. methyl methoxyacetate, methoxyacetic acid, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid, etc.)) ], 3-oxypropionic acid alkyl esters [for example, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid) Methyl, 3-ethoxypropionate, etc.)], 2-oxypropionic acid alkyl esters [for example, methyl 2-oxypropionate, 2-oxypropionate] Ethyl pionate, 2-oxypropionic acid propyl, and the like (e.g., methyl 2-methoxypropionate, 2-methoxy ethylpropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate) ], Methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.). ), Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetic acid, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like and ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol hair Butyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like and ketones, for example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3 Examples of -heptanone and the like and aromatic hydrocarbons include toluene and xylene.

An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

When using in combination of 2 or more types of organic solvents, Especially preferably, the said 3-ethoxy propionate methyl, 3-ethoxy propionate ethyl, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-meth It is a mixed solution consisting of two or more selected from methyl oxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate.

As the quantity of the organic solvent contained in a colored radiation-sensitive composition, it is preferable that it is 10 mass%-90 mass% with respect to the whole quantity of a colored radiation-sensitive composition, It is more preferable that it is 20 mass%-80 mass%, 25 mass It is more preferable that it is% -75 mass%.

<Increase / decrease>

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 wavelength of the photosensitive wavelength. As a sensitizer, the sensitizer which has an absorption wavelength in the wavelength range of 300 nm-450 nm is mentioned.

As the sensitizer, for example, polynuclear aromatics such as phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene, for example fluorescein, eosin, erythrosin, rhodamine B, rose Xanthenes such as bengal, thioxanthones, cyanines, merocyanines, phthalocyanines, for example thiazines such as thionine, methylene blue, toluidine blue, acridines, anthraquinones, squalanes, Coumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazoles, porphyrins, spiro compounds, quinacridones, indigo, styryls, Pyryllium compounds, pyrromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, for example, barbituric acid derivatives, thiobarbituric acid derivatives, aromatic ketone compounds such as acetophenone, benzophenone, mihilerketone, N- Ah And the like heterocyclic compounds, such as the oxazolidinone.

<Chain transfer agent>

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

<Alkali-soluble resin>

It is also preferable that the colored radiation-sensitive composition of this invention contains alkali-soluble resin from which the structure differs from (B) specific resin. By containing the said alkali-soluble resin, developability and pattern formation property further improve.

When specific resin has an acidic radical and shows alkali solubility, although specific resin is alkali-soluble resin here, alkali-soluble resin from which a structure differs from a specific resin is demonstrated below.

The alkali-soluble resin may be a linear organic polymer having a structure different from that of the specific resin, and an alkali-soluble resin having a group that promotes at least one alkali solubility in a molecule (preferably an acrylic copolymer or a molecule having a styrene copolymer as a main chain). It can select suitably from resin.

As alkali-soluble resin in this invention, it is preferable to use at least one of the linear organic polymer polymer which shows alkali solubility in specific resin, and a structure different from a specific resin, and may contain both.

As the linear organic polymer having a different structure from the specific resin, from the viewpoint of heat resistance, polyhydroxy styrene resin, polysiloxane resin, acrylic resin, acrylamide resin and acryl / acrylamide copolymer resin are preferred, and developability control is possible. From a viewpoint of acrylic resin, acrylamide resin, and acryl / acrylamide copolymer resin are preferable.

Examples of the group which promotes alkali solubility (hereinafter also referred to as acid group) include carboxyl group, phosphoric acid group, sulfonic acid group, phenolic hydroxyl group, and the like, but are soluble in an organic solvent and preferably developable by a weak alkaline aqueous solution. Acrylic acid is mentioned as especially preferable. These acid groups may be only one type, or may be two or more types.

As a monomer which can provide an acidic radical after the said superposition | polymerization, the monomer which has hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, the monomer which has epoxy groups, such as glycidyl (meth) acrylate, and 2-isocyanate ethyl, for example. The monomer etc. which have isocyanate groups, such as (meth) acrylate, etc. are mentioned. There may be only one type of monomers for introducing these acid groups, or two or more types thereof. In order to introduce an acid group into the 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 a “monomer for introducing an acid group”) may be polymerized as a monomer component. Do it. Moreover, when introduce | transducing an acidic radical as a monomer component the monomer which can provide an acidic radical after superposition | polymerization, the process for providing the acidic radical mentioned later, for example after polymerization is needed.

A well-known method of radical polymerization can be applied to manufacture of alkali-soluble resin which is a linear organic high molecular polymer different from specific resin, for example. The polymerization conditions such as the temperature, pressure, the kind and amount of the radical initiator, the kind of the solvent, and the like when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, and the conditions can be determined experimentally. .

As alkali-soluble resin which is a linear organic high molecular polymer different from specific resin, the polymer which has a carboxylic acid in a side chain is preferable, A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, maleic acid Alkyl-soluble phenol resins, such as a copolymer, a partially esterified maleic acid copolymer, a novolak-type resin, etc., and the acid cellulose derivative which has a carboxylic acid in a side chain, and what added an acid anhydride to the polymer which has a hydroxyl group are mentioned. In particular, the copolymer of (meth) acrylic acid and the other monomer copolymerizable with this is preferable as alkali-soluble resin. As another monomer copolymerizable with (meth) acrylic acid, an alkyl (meth) acrylate, an aryl (meth) acrylate, a vinyl compound, etc. are mentioned. 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, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, As vinyl compounds, such as cyclohexyl (meth) acrylate, styrene, (alpha) -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate , N-phenylmaleimide and N- as N-substituted maleimide monomers described in Japanese Patent Application Laid-Open No. 10-300922, such as polystyrene macromonomer and polymethyl methacrylate macromonomer. Claw-hexyl may be mentioned maleimide and the like. In addition, the other monomer copolymerizable with these (meth) acrylic acid may be only 1 type, or 2 or more types may be sufficient as it.

As alkali-soluble phenol resin, when the coloring photosensitive composition of this invention is made into a positive composition, it can be used preferably. As an alkali-soluble phenol resin, a novolak resin or a vinyl polymer etc. are mentioned, for example.

As said novolak resin, what is obtained by condensing phenols and aldehydes in presence of an acid catalyst is mentioned, for example. Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol or bisphenol A.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and the like.

The said phenols and aldehydes can be used individually or in combination of 2 or more types.

As a specific example of the said novolak resin, the condensation product of methacresol, paracresol, or a mixture thereof and formalin is mentioned, for example.

The said novolak resin may adjust molecular weight distribution using means, such as a fractionation. Moreover, you may mix low molecular weight components which have phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with the said novolak resin.

Moreover, you may use alkali-soluble resin which has a polymeric group in order to improve the crosslinking efficiency of the colored radiation-sensitive composition in this invention. As alkali-soluble resin which has a polymeric group, alkali-soluble resin etc. which contained an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in a side chain are useful. Examples of the polymer containing the polymerizable group described above include Diamond NR series (manufactured by Mitsubishi Rayon Corporation), Photomer6173 (manufactured by COOH-containing polyurethane acrylic oligomer.Diamond Shamrock Co. Ltd.), biscot R-264, KS resist 106 (All of which are made by Osaka Organic Kagaku Kogyo KK), the Pyclomer P series, the Flaccel CF200 series (all made by Daicel Kagaku Kogyo KK), Ebecryl3800 (DAICEL-UCB Company LTD.), And the like.

As alkali-soluble resin containing these polymerizable groups, urethane obtained by reacting an isocyanate group and an OH group previously, leaving one unreacted isocyanate group, and also by the reaction of the compound containing a (meth) acryloyl group, and the acrylic resin containing a carboxyl group is carried out. An unsaturated group-containing acrylic resin, an acid pendant epoxy acrylate resin, and an OH group obtained by the reaction of a modified polymerizable double bond-containing acrylic resin and an acrylic resin containing a carboxyl group and a compound having an epoxy group and a polymerizable double bond in the molecule. A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing a dibasic acid anhydride having a polymerizable double bond, an acrylic resin containing an OH group, and a resin obtained by reacting a compound having an isocyanate and a polymerizable group, Japanese Patent Laid-Open No. 2002- Japanese Patent No. 229207 and Japanese Patent Resin obtained by performing basic treatment with resin which has ester group which has a leaving group, such as a halogen atom or a sulfonate group, in a (alpha) position or (beta) position described in Unexamined-Japanese-Patent No. 2003-335814 in a side chain is preferable.

Especially as a alkali-soluble resin, the benzyl (meth) acrylate / (meth) acrylic acid copolymer and the benzyl (meth) acrylate / (meth) acrylic acid / other multicomponent copolymer which consists of other monomers are preferable. In addition, 2-hydroxyethyl methacrylate copolymerized, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid described in JP-A-7-140654 Copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate The rate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. are mentioned.

The acid value of the alkali-soluble resin which is a linear organic polymer having a structure different from the specific resin is preferably 30 mg KOH / g to 200 mg KOH / g, more preferably 50 mg KOH / g to 150 mg KOH / g. It is preferable and it is most preferable that it is 70-120 mgKOH / g.

Moreover, as a weight average molecular weight (Mw) of alkali-soluble resin which is a linear organic high molecular polymer different from specific resin, 2,000-50,000 are preferable, 5,000-30,000 are more preferable, 7,000-20,000 are the most preferable.

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

<Polymerization inhibitor>

In the colored radiation-sensitive composition of the present invention, it is preferable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored radiation-sensitive composition.

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-t-butylphenol), N-nitrosophenylhydroxyamine 1st cerium salt, etc. are mentioned. Especially, p-methoxy phenol is preferable.

As for the addition amount of a polymerization inhibitor, about 0.01 mass%-about 5 mass% are preferable with respect to the mass of a colored radiation-sensitive composition.

<Substrate adhesive>

In addition, in this invention, you may add the board | substrate adhesive agent which can improve board | substrate adhesiveness to a colored radiation-sensitive composition.

It is preferable to use a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent as a board | substrate adhesive agent. As a silane coupling agent, (gamma) -methacryloxypropyl trimethoxysilane, (gamma) -methacryloxypropyl triethoxysilane, (gamma) -acryloxypropyl trimethoxysilane, (gamma) -acryloxypropyl triethoxysilane, (gamma) -mercaptopropyl trimethoxysilane, (gamma) -aminopropyl triethoxysilane, phenyl trimethoxysilane, etc. are mentioned. Especially, as a board | substrate adhesive agent, (gamma) -methacryloxypropyl trimethoxysilane is preferable.

It is preferable that content of a board | substrate adhesive agent is 0.1 mass% or more and 30 mass% or less with respect to the total solid of the radiation sensitive composition of this invention from a viewpoint that a residue does not remain in an unexposed part when exposing and developing colored radiation-sensitive composition. It is more preferable that they are 0.5 mass% or more and 20 mass% or less, and it is especially preferable that they are 1 mass% or more and 10 mass% or less.

<Surfactant>

You may add various surfactant to the colored radiation-sensitive composition of this invention from a viewpoint of further improving applicability | paintability. As surfactant, various surfactant, such as a fluorochemical surfactant, nonionic surfactant, cationic surfactant, anionic surfactant, silicone type surfactant, can be used.

In particular, the colored radiation-sensitive composition of the present invention further improves the uniformity of the coating thickness and the liquid saving property in that the liquid properties (particularly, fluidity) when prepared as a coating liquid are further improved by containing a fluorine-based surfactant. Can be.

That is, when forming a film using the coating liquid to which the coloring radiation-sensitive composition containing a fluorine-type surfactant is applied, the wettability to a to-be-coated surface is improved by reducing the interfacial tension of a to-be-coated surface and a coating liquid. The applicability is improved. For this reason, even when a thin film of several micrometers is formed with a small amount of liquid, it is effective at the point which can form the film of uniform thickness with small thickness nonuniformity more preferably.

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

Examples of the fluorine-based surfactants include Mega Pack F171, Copper F172, Copper F173, Copper F176, Copper F177, Copper F141, Copper F142, Copper F143, Copper F144, Copper R30, Copper F437, Copper F475, Copper F479, Copper F482, East F554, East F780, East F781 (above, made by DIC Corporation), Fluoride FC430, East FC431, East FC171 (above, manufactured by Sumitomo 3M), Surflon S-382, East SC-101, East SC-103, East SC-104, East SC-105, East SC1068, East SC-381, East SC-383, East S393, East KH-40 (above, manufactured by Asahi Glass Co., Ltd.). have.

Specific examples of the nonionic surfactants include glycerol, trimethylolpropane, trimethylol ethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate, etc.) and 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 (flu of BASF Corporation make) Lonic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Solsperth 20000 (manufactured by Nihon Lubrizol), Pionine D-6112- W (Takemoto Yushi Co., Ltd. product) etc. are mentioned.

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.), and (meth) acrylic acid copolymer polyflow. No. 75, No. 90, No. 95 (manufactured by Kyoeisha Kagaku Co., Ltd.), W001 (Yusho Co., Ltd.), etc. are mentioned.

Specific examples of the anionic surfactants include W004, W005, and W017 (manufactured by Yusho Corporation).

As a silicone type surfactant, Toray silicon DC3PA, Toray silicon SH7PA, Toray silicon DC11PA, Toray silicon SH21PA, Toray silicon SH28PA, Toray silicon SH29PA, Toray silicon SH30PA, Toray silicon SH8400 (above, Toray Dow Corning Corporation make) , TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (more than Momentive Performance Materials, Inc.), KP341, KF6001, KF6002 (more, made by Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323 , BYK330 (above, made by Big Chemistry Co., Ltd.), and the like.

The surfactant may be used alone or in combination of two or more.

As for the addition amount of surfactant, 0.001 mass%-2.0 mass% are preferable with respect to the total mass of a colored radiation-sensitive composition, More preferably, it is 0.005 mass%-1.0 mass%.

<Other Ingredients>

In the colored radiation-sensitive composition of the present invention, if necessary, chain transfer agents such as alkyl esters of N, N-dialkylaminobenzoic acid and 2-mercaptobenzothiazole, thermal polymerization initiators such as azo compounds and peroxide compounds, and thermal polymerization Plasticizers such as polyfunctional thiols, epoxy compounds, and dioctylphthalate, developability agents such as low molecular weight organic carboxylic acids, other fillers, polymers other than the specific binders and alkali-soluble resins for the purpose of improving the components, membrane strength and sensitivity. Various additives, such as a compound, antioxidant, and agglutination agent, can be contained.

In addition, a thermosetting agent may be added to increase the degree of curing of the film by post-heating after development. As a thermosetting agent, thermal polymerization initiators, such as an azo compound and a peroxide, a novolak resin, a resol resin, an epoxy compound, a styrene compound, etc. are mentioned.

Preparation of colored radiation-sensitive composition

It is preferable to prepare the colored radiation-sensitive composition of this invention using the organic solvent with each component of said (A)-(D) and components other than what is used according to desire.

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

The colored radiation-sensitive composition of the present invention is excellent in pigment dispersion stability and developability even if it contains a high concentration of fine pigments, and thus can produce colored regions having good color characteristics with high precision. Especially when the film thickness is 0.8 micrometer or less, Preferably the pixel of the range of 0.1 micrometer-0.5 micrometers is formed, the effect is remarkable.

Since the colored radiation-sensitive composition of the present invention has excellent dispersion stability, it is possible to form a thin film when applied to the formation of a color filter included in a liquid crystal display device having excellent color reproducibility or a solid-state image sensor having excellent resolution. Since it is advantageous, in the said use, it is preferable to prepare in the form which contained the pigment in high concentration.

It is preferable to filter the colored radiation-sensitive composition of the present invention with a filter for the purpose of removing foreign matters or reducing defects. As a filter, if it is conventionally used for a filtration use etc., it can be used without particular limitation. For example, a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon-6 or nylon-6,6, a polyolefin resin such as polyethylene or polypropylene (PP) And the like). Of these materials, polypropylene (including high-density polypropylene) is preferable.

The hole diameter of the filter is preferably 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 reliably remove the fine foreign material which inhibits preparation of the uniform and smooth colored radiation-sensitive composition in a post process.

When using a filter, you may combine another filter. In that case, the filtering by a 1st filter may be only once, and may be performed twice or more.

It is also possible to combine the first filters having different hole diameters within the above-mentioned range. The hole diameter here can refer to the nominal value of the filter maker. As a commercially available filter, for example, Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microless Co., Ltd.) or Kitsuki Co., Ltd. can be selected from various filters provided. have.

The second filter may be formed of the same material as the first filter described above.

For example, the filtering in the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing the other components.

[Color filter and its manufacturing method]

Next, the color filter of this invention and its manufacturing method are demonstrated.

The color filter of this invention has a coloring area (coloring pattern) formed by giving the coloring radiation-sensitive composition of this invention on a board | substrate. It is characterized by the above-mentioned.

Hereinafter, the color filter of this invention is demonstrated in detail through the manufacturing method (manufacturing method of the color filter of this invention).

The manufacturing method of the color filter of this invention provides the radiation sensitive composition of this invention on a board | substrate, and forms a radiation sensitive composition layer (coloring layer), and the said radiation sensitive composition layer It includes the process of exposing in a pattern form (exposure process), and the process (development process) of developing the said radiation sensitive composition layer after exposure, and coloring pattern molding.

<Color layer forming process>

In a colored layer formation process, the colored radiation-sensitive composition of this invention is apply | coated on a board | substrate, and the colored layer (radiation-sensitive composition layer) which consists of said colored radiation-sensitive composition is formed.

As a substrate which can be used for this process, for example, an alkali free glass, soda glass, Pyrex (registered trademark) used for photoelectric conversion element substrates in a CCD or CMOS, a silicon substrate, a liquid crystal display device, etc. used for a solid-state image sensor, etc. Glass, quartz glass, and the thing which adhered the transparent conductive film to these, etc. are mentioned. These board | substrates may be provided with the black matrix which isolate | separates each pixel.

Moreover, you may form a primer layer on these board | substrates for adhesion improvement with an upper layer, prevention of a material diffusion, or planarization of the surface of a board | substrate as needed.

As a coating method of the colored radiation-sensitive composition of this invention on a board | substrate, various coating methods, such as a slit coating, an inkjet method, a rotary coating, cast coating, roll coating, and screen printing, can be applied.

Drying (prebaking) of the colored layer (colored radiation-sensitive composition layer) apply | coated on the board | substrate can be performed in 10 to 300 second at the temperature of 50 degreeC-140 degreeC with a hotplate, oven, etc.

As the coating film thickness (hereinafter referred to as "dry film thickness" suitably) after drying of a colored layer, the viewpoint of a color density ensuring, the light of a diagonal direction does not reach a light receiving part, and the difference of the light condensation rate becomes remarkable at the stage and center of a device, etc. 0.05 micrometers or more and less than 1.0 micrometer are preferable from a viewpoint of reducing the problem of this, 0.1 micrometers or more and 0.8 micrometers or less are more preferable, 0.2 micrometers or more and 0.7 micrometers or less are especially preferable.

Exposure process

In an exposure process, the colored layer (irradiation composition layer) formed in the said colored layer formation process is exposed in pattern form.

In exposure in this process, it is preferable to perform exposure of a colored layer by exposing through a predetermined | prescribed mask pattern and hardening only the coating film part irradiated with light. Especially as radiation which can be used in exposure, radiation, such as g line | wire, h line | wire, i line | wire, is used preferably. 30mJ / cm <2> -1500mJ / cm <2> is preferable, 50mJ / cm <2> -1000mJ / cm <2> of an irradiation amount is more preferable, and 80mJ / cm <2> -500mJ / cm <2> is the most preferable.

Development Process

By performing an alkali developing process (development process) following an exposure process, the uncured part after exposure is eluted to a developing solution, and the photocured part remains. By this developing step, a patterned epithelium consisting of pixels of each color (for example, three colors or four colors) can be formed.

The developing method may be any of a dipping method, a shower method, a spray method, a paddle method, and the like, and a swing method, a spin method, an ultrasonic method, or the like may be combined therewith.

Before the contact with the developer, the surface to be developed may be wetted with water or the like beforehand to prevent development stains.

As the developing solution, an organic alkali developing solution which does not cause damages to a circuit of a ground (ground) is preferable. As image development temperature, it is 20 degreeC-30 degreeC normally, and developing time is 20 to 90 second.

As an alkaline agent which a developing solution contains, for example, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabi Organic alkaline compounds, such as cyclo- [5,4,0] -7-undecene, inorganic compounds, such as sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, etc. are mentioned.

As a developing solution, the alkaline aqueous solution which diluted these alkali chemicals with pure water so that a density | concentration may be 0.001 mass%-10 mass%, Preferably it is 0.01 mass%-1 mass% is used preferably. In addition, when the developing solution which consists of such alkaline aqueous solution is used, it generally washes (rinses) with pure water after image development.

Subsequently, the excess developer is washed off and dried.

Moreover, in the manufacturing method of this invention, even after performing the above-mentioned colored layer formation process, exposure process, and image development process, the hardening process of hardening the coloring pattern formed as needed by post-heating (post-baking) or post-exposure is included. good. Post-baking is the heat processing after image development for making hardening perfect, and the thermosetting process of 100 degreeC-270 degreeC is normally performed. In the case of using light, it can be performed by g-ray, h-ray, i-ray, excimer laser such as KrF or ArF, electron beam, X-ray, etc. As time, they are 10 second-180 second, Preferably they are 30 second-60 second. In the case of the combination of post-exposure and post-heating, post-exposure is preferably performed first.

The color filter containing a desired color is produced by repeating the above-mentioned colored layer formation process, exposure process, and image development process (it is also a hardening process as needed) by the desired number of colors.

Since the color filter of this invention is manufactured using the coloring radiation sensitive composition of this invention excellent also in exposure sensitivity, the hardened composition in an exposure part is excellent in adhesiveness and developability with a board | substrate, and the formed colored pattern and board | substrate The adhesiveness of 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 removed by using a known cleaning liquid even when it is attached to, for example, a nozzle of an application device discharge part, a piping part of an application device, an inside of an application device, and the like. In this case, in order to perform more efficient washing removal, it is preferable to use the above-mentioned organic solvent as a washing | cleaning liquid as the organic solvent contained in the colored radiation-sensitive composition of this invention.

Further, Japanese Patent Laid-Open No. 7-128867, Japanese Patent Laid-Open No. 7-146562, Japanese Patent Laid-Open No. 8-278637, Japanese Patent Laid-Open No. 2000-273370, Japanese Patent Laid-Open No. 2006-85140, The cleaning liquids described in Japanese Patent Application Laid-Open No. 2006-291191, Japanese Patent Application Laid-Open No. 2007-2101, Japanese Patent Application Laid-Open No. 2007-2102, Japanese Patent Application Laid-Open No. 2007-281523, and the like also wash and remove the colored radiation-sensitive composition of the present invention. It can use suitably as a wash liquid for solvents.

It is preferable to use alkylene glycol monoalkyl ether carboxylate or alkylene glycol monoalkyl ether as a washing | cleaning liquid.

These organic solvents used as washing | cleaning liquid may be used individually, or may mix and use 2 or more types.

When mixing 2 or more types of organic solvents, the mixed solvent which mixes 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 which has a hydroxyl group, and the organic solvent which does not have a hydroxyl group is 1 / 99-99 / 1, Preferably it is 10 / 90-90 / 10, More preferably, it is 20 / 80-80 / 20. As a mixed solvent, it is especially preferable that the ratio is 60/40 in the mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME).

Moreover, in order to improve the permeability of the washing | cleaning liquid with respect to a colored radiation-sensitive composition, you may add surfactant mentioned above as surfactant which a colored radiation-sensitive composition can contain to a washing | cleaning liquid.

Moreover, the color filter of this invention manufactured by the manufacturing method of the color filter of this invention can be used suitably for solid-state image sensors, such as CCD and CMOS, Moreover, image display devices, such as electronic paper and organic EL, and a liquid crystal display device It can also be used preferably. It is especially suitable for the solid-state image sensor of CCD and CMOS of high resolution exceeding 1 million pixels. The color filter of this invention can be used also as a color filter arrange | positioned, for example between the light receiving part of each pixel which comprises a CCD element, and a microlens for condensing.

[Solid State Imaging Device]

The solid-state image sensor of this invention is equipped with the color filter of this invention. Although the structure of the solid-state image sensor of this invention is a structure with which the color filter for solid-state image sensors of this invention is equipped, and if it is a structure which functions as a solid-state image sensor, there is no limitation in particular, For example, the following structures are mentioned.

It has a transfer electrode which consists of several photodiodes, polysilicon, etc. which comprise the light reception area | region of a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) on a board | substrate, The light reception part of a photodiode on the said photodiode and the said transfer electrode Has a light shielding film made of tungsten or the like opened only, a device protective film made of silicon nitride or the like formed on the light shielding film to cover the entire surface of the light shielding film and the photodiode light receiving unit, and has a color filter for a solid-state imaging device of the present invention on the device protective film. Configuration.

Moreover, the structure which has condensing means (for example, a microlens etc .. or the same below) on the said device protective layer under the color filter (side close to a support body), or the structure which has condensing means on a color filter may be sufficient.

Example

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the main scope thereof is exceeded. In addition, "part" and "%" are mass references | standards unless there is particular notice.

[Production of Silicon Wafer with Primer Layer]

The composition for primer layers was prepared with the composition of the following composition for primer layers, it apply | coated uniformly on a silicon wafer by spin coating, the coating film was formed, and the formed coating film was heat-processed for 120 second on the 230 degreeC hotplate. In addition, the application | coating rotation speed of a spin coat was adjusted so that the film thickness of the coating film after heat processing might be set to about 0.1 micrometer. In this way, the silicon wafer with a primer layer in which the primer layer was formed on the silicon wafer was obtained.

(Composition of Composition for Primer Layer)

Organic solvent: 54.56 parts of propylene glycol methyl ether acetate (hereinafter referred to as PGMEA)

Organic solvent: 32.42 parts of ethoxyethyl propionate (hereinafter referred to as EEP)

Binder: 12.19 parts of Daicel Corporation make, a brand name cyclomer PCR-1000

Fluorine-based surfactant: DIC Corporation, trade name Megapack F-781, 0.83 parts of 0.2% EEP solution

[Preparation of Red Pigment Dispersion]

The mixture of the following composition was mixed and dispersed for 3 hours in a bead mill (high pressure disperser NANO-3000-10 (manufactured by Nihon Biei Co., Ltd.) with a pressure reducing mechanism) using 0.3 mm diameter zirconia beads. -1 was prepared.

(Furtherance)

Red pigment: C.I. Pigment Red 254 Part 4.74

Yellow pigment: C.I. Pigment Yellow, part 139

Dispersion resin: Nippon Shokubai Co., Ltd. make, brand name: Acricure RD-F8 4.69 parts

Organic solvents: 51.75 parts of PGMEA

[Preparation of Green Pigment Dispersion]

Pigment dispersion liquid G was mixed and dispersed for 3 hours in a bead mill (high pressure disperser NANO-3000-10 (manufactured by Nihon Biei Co., Ltd.) with a pressure reduction mechanism) using 0.3 mm diameter zirconia beads. -1 was prepared.

(Furtherance)

Green pigment: C.I. P pigment green 36 part 2.26

Yellow pigment: C.I. Pigment Yellow 150 Part 2.19

Dispersion resin: Fujikura Kasei Co., Ltd. make, brand name: Acrives FFS-6824 (molecular weight 10000) 3.09 parts

Organic solvents: PGMEA 28.99 parts

Organic solvent: 2.36 parts of cyclohexanone

[Preparation of green colored radiation-sensitive composition]

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.

(Furtherance)

Organic solvents: 47.06 parts of PGMEA

Resin: 5.94 parts of A-1

Polymerizable compound: 2.05 parts of A-DPH-12E (following C-1) made by Nippon Kayaku Co., Ltd.

Polymerizable compound: Nippon Kayaku Co., Ltd., KAYARAD DPHA (Dipentaerythritol hexa acrylate) 0.69 parts

Photoinitiator: 0.34 part made by BASF, Irgacure OXE-02 (following E-1)

Pigment dispersion liquid G-1 38.89 parts

Fluorine-based surfactants: 4.17 parts of DIC Corporation, trade name Megapack F-781, 0.2% PGMEA solution

Nonionic surfactant: Takemoto Yushi Co., Ltd., pionein D-6112-W 0.18 parts

UV absorber: 0.72 parts of D-1

Polymerization inhibitor: 0.001 part of p-methoxyphenol

[Production of Substrate Having Green Coloring Pattern]

The green colored radiation-sensitive composition obtained above was apply | coated so that the film thickness after drying of a colored layer might be 0.4 micrometer on the primer layer of the silicon wafer substrate with a primer layer, and the radiation-sensitive colored layer was formed. And heat processing (prebaking) was performed for 120 second using the 100 degreeC hotplate. Subsequently, using i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Co., Ltd.), light having a wavelength of 365 nm was exposed to a colored layer at an exposure dose of 300 mJ / cm 2 through a Bayer pattern mask having a pattern of 1.4 µm x 1.4 µm. 200 patterns were irradiated on the whole wafer surface. Subsequently, the silicon wafer substrate on which the colored layer is formed is placed on a horizontal rotating table of a spin shower developer (DW-30 type; manufactured by Chemitronics Co., Ltd.), and alkali developer CD-2060 (Fuji Film Electronics Materials) Paddle development was carried out at room temperature for 60 second using the product made from Corporation | Co., Ltd., the green coloring pattern was formed in the silicon wafer substrate, and it heat-processed (post-baking) for 5 minutes on the 220 degreeC hotplate.

In this way, the board | substrate which has a green coloring pattern was produced.

Example 1

[Preparation of red colored radiation-sensitive composition]

The colored radiation-sensitive composition of Example 1 was prepared with the following composition.

(Furtherance)

Organic solvents: 25.2 parts of PGMEA

Organic solvents: EEP 1.67 parts

Specific resin: 0.74 parts of following B-1 (molecular weight 18000, composition ratio is mol%)

Polymerizable compound: Nippon Kayaku Co., Ltd., 3.37 parts of A-DPH-12E (C-1)

Photoinitiator: 0.89 parts of Irgacure OXE-01 (following E-2), manufactured by BASF Corporation

Pigment dispersion: 63.29 parts of the above R-1

Fluorine-based surfactant: 4.17 parts of DIC Corporation, brand name Megapack F-781, 0.2% EEP solution

Nonionic surfactant: Takemoto Yushi Co., Ltd., pionein D-6112-W 0.17 parts

Ultraviolet absorber: 0.50 parts of the above D-1

Polymerization inhibitor: 0.002 parts of p-methoxyphenol

[Formation of Red Pattern on Silicon Wafer Substrate with Primer Layer]

The red colored radiation-sensitive composition obtained above was apply | coated so that the dry film thickness of a colored layer might be about 0.8 micrometer on the primer layer of the silicon wafer substrate with a primer layer, and the radiation-sensitive colored layer was formed. And it heat-processed (prebaked) for 120 second using the 100 degreeC hotplate. Subsequently, using i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Co., Ltd.), the light having a wavelength of 365 nm was 1 cm at an exposure dose of 400 mJ / cm 2 to the colored layer through an island pattern mask of 1.4 μm × 1.4 μm. About 200 repeating patterns of * 1 cm were irradiated. Subsequently, the silicon wafer substrate on which the colored layer is formed is placed on a horizontal rotating table of a spin shower developer (DW-30 type; manufactured by Chemitronics Co., Ltd.), and alkali developer CD-2060 (Fuji Film Electronics Materials) Paddle development was carried out at room temperature for 60 second using (Corporation Co., Ltd.), and the red coloring pattern was formed in the silicon wafer substrate.

A silicon wafer substrate having a red colored pattern formed thereon is fixed to the horizontal rotating table by a vacuum chuck method, and pure water is supplied from a jet nozzle from above the center of rotation by rinsing while rotating the silicon wafer substrate at a rotational speed of 800 rpm by a rotating device. The process was performed, and it spin-dried after that and obtained the color filter which has a red coloring pattern.

All the formed red coloring patterns are square, and the cross section shows the favorable profile which is rectangular shape, and it turns out that it is a color filter suitable for a solid-state image sensor.

[Evaluation of residues]

The silicon wafer with the red colored pattern obtained above was observed using an optical microscope (manufactured by Olympus) to observe a repeating pattern of 1 cm × 1 cm formed in an objective lens 5 times, an eyepiece 10 times and a bright field, The presence or absence of the residue in a coloring pattern formation part was evaluated on the following criteria. The results are collectively shown in Table 4.

<Judge criteria>

Die rate with residue is made by using a mask of fine pattern to make several groups of the same pattern in 100 groups of 10 rows x 10 columns at 1cm × 1cm, and count the groups where the residues are observed among the 100 groups. Will pay off.

[Formation of Red Coloring Pattern on Substrate Having Green Coloring Pattern]

The red colored radiation sensitive composition obtained above was apply | coated so that the film thickness after drying of a red colored layer might be 0.6 micrometer on the silicon wafer substrate which has a green coloring pattern, and the radiation sensitive colored layer was formed. And heat processing (prebaking) was performed for 120 second using the 100 degreeC hotplate. Subsequently, using i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Corporation), light of 365 nm wavelength was exposed in a range of 50 to 1050 mJ / cm 2 through an island pattern mask having a pattern of 1.4 µm x 1.4 µm. Was changed by 50 mJ / cm 2 and irradiated between the green pattern and the green pattern. 200 patterns were irradiated to the whole board | substrate whole surface. Subsequently, the silicon wafer substrate on which the colored layer is formed is placed on a horizontal rotating table of a spin shower developer (DW-30 type; manufactured by Chemitronics Co., Ltd.), and alkali developer CD-2060 (Fuji Film Electronics Materials) Paddle development was carried out at room temperature for 60 seconds using (manufactured by Co., Ltd.), and a red colored pattern was formed on a silicon wafer substrate having a green colored pattern, followed by heat treatment (post baking) for 5 minutes on a hot plate at 220 ° C. . In this way, a silicon wafer substrate having green and red colored patterns was obtained.

(Linearity evaluation)

The silicon wafer substrates having the green and red colored patterns obtained above were observed using a electron microscope (S-9260A, manufactured by Hitachi Hi-Tech Co., Ltd.) at a magnification of 20000x with a red exposure pattern formed at an exposure dose of Eopt. The linearity of the edge part of the island pattern of was evaluated by the following criteria.

Eopt is the optimum exposure dose. When the exposure amount is increased, the size of the pattern becomes larger than that of the mask, so that the exposure amount is gradually increased to form the pattern at the same size as the mask, and the exposure amount without peeling after development. The results are collectively shown in Table 4.

<Judge criteria>

[Example 2]

In the preparation of the red colored radiation-sensitive composition of Example 1, except for changing the specific resin B-1 to B-2 (the following structure: molecular weight 19000, the composition ratio is mol%), the red coloration feeling was performed in the same manner as in Example 1. The radioactive 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, a red colored radiation-sensitive composition is prepared in the same manner as in Example 1 except that the polymerizable compound C-1 is changed to C-2 (the following structure), Moreover, it evaluated similarly to 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. It evaluated similarly.

[Examples 5-8]

In the preparation of the red colored radiation-sensitive composition of Example 1, the colored radiation-sensitive composition of Examples 5 to 8 was produced in the same manner as in Example 1 except that the amount of the ultraviolet absorbent was changed as in Table 4 below.

Comparative Example 1

In the preparation of the red colored radiation-sensitive composition of Example 4, except that the ultraviolet absorbent D-1 was not added, a red colored radiation-sensitive composition was prepared in the same manner as in Example 4, and evaluated in the same manner as in Example 1 did.

Comparative Example 2

In the preparation of the red colored radiation-sensitive composition of Example 2, except that the ultraviolet absorbent D-1 was not added, a red colored radiation-sensitive composition was prepared in the same manner as in Example 2, and evaluated in the same manner as in Example 1 did.

[Comparative Example 3]

In the preparation of the red colored radiation-sensitive composition of Example 3, except that the ultraviolet absorbent D-1 was not added, 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 did.

[Comparative Example 4]

In the preparation of the red colored radiation-sensitive composition of Example 1, except that the ultraviolet absorbent D-1 was not added, a red colored radiation-sensitive composition was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1 did.

[Comparative Example 5]

In preparation of the red colored radiation-sensitive composition of Example 3, specific resin B-1 is changed into B-3 (following structure) without adding the ultraviolet absorber D-1, and it is the same as that of Example 3 except others. Thus, the red colored radiation-sensitive composition was prepared, 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 is not added, and the specific resin B-1 is changed to B-3, and the red coloring is performed in the same manner as in Example 1 otherwise. The radiation sensitive composition was prepared and evaluated similarly to Example 1.

[Example 9]

In the preparation of the red colored radiation-sensitive composition of Example 1, the polymerizable compound C-1 is changed to C-3 (the following structure), and in the same manner as in Example 1, a red colored radiation-sensitive composition is 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 is changed to C-4 (the following structure), and in the same manner as in Example 1, a red colored radiation-sensitive composition is 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 KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., except that it was the same as in Example 1 except that the red colored radiation-sensitive composition was used. The 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 colored radiation-sensitive composition of Comparative Example 7 was produced in the same manner as in Example 1 except that the specific resin and the polymerizable compound were changed as in Table 4 below.

Table 4 shows the following.

Examples 1 to 11 using the colored radiation-sensitive composition containing the specific resin, the polymerizable compound and the ultraviolet absorber of the present invention are both residue and linear compared to Comparative Examples 1 to 7 lacking any one of these compounds. Excellent in terms of improving the In particular, Example 1, 2, 6-10 which use C-1, C-3, or C-4 as a polymeric compound and contain 1-5 mass% of total solids of a colored radiation-sensitive composition using a ultraviolet absorber It can be seen that remarkably improved in both the residue and the linearity.

<Production of color filter>

Preparation of blue colored radiation-sensitive composition

The following components were mixed, and the mixture was stirred for 3 hours at a rotational speed of 3,000 r.p.m. using a homogenizer to prepare a mixed solution containing a pigment.

Pigment: C.I. Pigment Blue 15: 6 95

Pigment derivative: 15 parts of the following compound

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

750 parts of PGMEA

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

The following blue colored radiation-sensitive composition was produced using the pigment dispersion liquid (P-1) obtained above.

Pigment Dispersion: (P-1) 1000 parts

Polymerizable compound: 100 parts of KAYARAD DPHA (made by Nippon Kayaku)

Photoinitiator: 30 parts of 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oximes

Resin: 100 parts of A-1 above

Solvent: PGMEA 300 parts

The colored pattern of red (R) of 1.6 * 1.6 micrometer was formed on the wafer using the red colored radiation-sensitive composition of Example 6 obtained above. Similarly, using the green colored radiation-sensitive composition obtained as described above, green (G) having 1.6 × 1.6 μm and the colored colored radiation pattern of blue (B) are sequentially formed using the colored colored radiation-sensitive composition. Thus, the color filter for solid-state image sensors was produced.

-evaluation-

As a result of attaching a full color color filter to the solid-state image pickup device, it was confirmed that the solid-state image pickup device had a high resolution and was excellent in color separation.

Claims (17)

(A) a coloring agent, (B) the acrylic resin which has a partial structure represented by following formula (I), (C) polymeric compound, and (D) ultraviolet absorber,
Content of said (D) ultraviolet absorber is 0.1 mass%-10 mass% with respect to solid content of a colored radiation-sensitive composition, The colored radiation-sensitive composition characterized by the above-mentioned.

[In formula (I), R represents a hydrogen atom or a monovalent substituent. * Represents the site | part of the bond with the main chain structure of an acrylic resin] The method of claim 1,
Content of the said (D) ultraviolet absorber is 1 mass%-5 mass% with respect to solid content of a colored radiation-sensitive composition, The colored radiation-sensitive composition characterized by the above-mentioned. 3. The method according to claim 1 or 2,
The said (C) polymeric compound is a polymeric radiation sensitive composition characterized by the polymeric compound containing an ethyleneoxy group and 5 or more acryloyl group or a methacryloyl group in a molecule | numerator. 3. The method according to claim 1 or 2,
The said (C) polymeric compound is represented by the following general formula (Z-1), The colored radiation-sensitive composition characterized by the above-mentioned.

[6 R of General Formula (Z-1) are all groups represented by the following General Formula (Z-2).]

[In 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.] 3. The method according to claim 1 or 2,
The colored radiation-sensitive composition characterized by the above-mentioned (B) acrylic resin which has a partial structure represented by Formula (I) is an acrylic resin containing a carboxyl group further. 3. The method according to claim 1 or 2,
(B) The acrylic resin having a partial structure represented by formula (I) is an acrylic resin derived from at least acryloyloxyethylureylenebenzoimidazole or methacryloyloxyethylureylenebenzoimidazole. Colored radiation-sensitive composition to be. 3. The method according to claim 1 or 2,
The acrylic resin which has the partial structure represented by said (B) Formula (I) is derived from at least acryloyloxyethylureylenebenzoimidazole or methacryloyloxyethylureylenebenzoimidazole, and acrylic acid or methacrylic acid. It is an acrylic resin, The coloring radiation sensitive composition characterized by the above-mentioned. 3. The method according to claim 1 or 2,
Content of the partial structure represented by Formula (I) contained in the acrylic resin which has a partial structure represented by said (B) Formula (I) is 1 mass%-30 mass% with respect to acrylic resin whole quantity, It is characterized by the above-mentioned. Colored radiation-sensitive composition. 3. The method according to claim 1 or 2,
The said (A) colorant is a red pigment, The coloring radiation-sensitive composition characterized by the above-mentioned. 3. The method according to claim 1 or 2,
The said (D) ultraviolet absorber is a compound represented by the following general formula (II), The colored radiation-sensitive composition characterized by the above-mentioned.

[In 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 simultaneously represent a hydrogen atom. There is nothing to indicate. Or R ¹ and R ² together with the nitrogen atom to which R ¹ and R ² bind form a cyclic amino group. R ³ and R ⁴ each independently represent a monovalent group. Or R ³ and R ⁴ combine with each other to form a ring] 11. The method of claim 10,
The said (D) ultraviolet absorber is a monovalent group represented by R <^3> and R <^4> in the said General formula (II), The colored radiation sensitive composition characterized by the above-mentioned. 3. The method according to claim 1 or 2,
The said (C) polymeric compound is a polymeric radiation sensitive composition characterized by the polymeric compound containing 3 or 4 acryloyl group or methacryloyl group in a molecule | numerator. 3. The method according to claim 1 or 2,
(E) The coloring radiation sensitive composition further containing a photoinitiator. The method of claim 13,
The said (E) photoinitiator is a colored radiation sensitive composition characterized by the above-mentioned. The color filter formed with the colored radiation-sensitive composition of Claim 1 or 2 is provided. The color filter characterized by the above-mentioned. The process of providing the colored radiation-sensitive composition of Claim 1 or 2 on a board | substrate, and forming 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 the exposure to form a colored pattern. The color filter of Claim 16 was provided. The solid-state image sensor characterized by the above-mentioned.