JP5679860B2 - Colored radiation-sensitive composition, color filter, method for producing the color filter, and solid-state imaging device - Google Patents

Description

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

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

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

  As a colorant in a color filter, since it has a clear color tone and high coloring power, a pigment is widely used. In particular, it is possible to use a pigment that has been miniaturized and exhibits suitable color separation properties. preferable.

  In recent years, in either a liquid crystal display or a solid-state imaging device, a fine colored pattern (for example, a colored pattern having a side of 2.0 μm or less on a solid-state imaging device) can be formed with good reproducibility for the purpose of improving resolution. At the same time, it is also required to reduce the thickness of the colored pattern (for example, 1 μm or less for a solid-state imaging device).

  As a method for producing a color filter for a liquid crystal display device having a high concentration and a low film thickness without deteriorating the image forming ability such as curability and the like with excellent adhesion to the substrate, ethylene dimer is essential as a dispersant. It has been proposed to use a colored resin composition using a polymer obtained by polymerizing a monomer component to be polymerized, and a graft copolymer and / or an acrylic block copolymer containing a nitrogen atom (for example, , See Patent Document 1). Moreover, about the polymer formed by superposing | polymerizing the monomer component which has ethylene dimer as an essential thing, forming the cured film which has transparency with heat resistance is proposed with the curable resin composition containing this ( (See Patent Document 2).

  Furthermore, in the production of a color filter with high color separation in a solid-state imaging device that requires high resolution, a pixel having a coloring power with high color purity in an ultra-thin layer having a color pixel thickness of 1 μm or less is required. There was a long-awaited improvement in technology.

JP 2006-161035 A JP 2004-300204 A

A colored cured film having a coloring power with high color purity even in a thin layer requires the colorability of the cured film itself, but in addition, color purity is reduced due to the following phenomenon.
For example, in the case of a multicolored cured film having colored pixels (hereinafter also simply referred to as “pixels”) such as a color filter, in order to form such a multicolored pixel, a pixel indicating one color is used. After forming, pixels having other colors need to be formed. At this time, a colored radiation-sensitive composition of another color (hereinafter referred to as “colored radiation-sensitive composition of the next color”) is applied on the previously formed pixel, and the previously obtained pixel is Pixels are sequentially formed at different locations by the colored radioactive composition of the next color. However, when pixels are sequentially formed using such a plurality of colored radioactive compositions, the colored radioactive composition of the next color remains as a residue on the previously formed pixels or is formed first. The colored radiation-sensitive composition of the next color penetrates into the formed pixels, resulting in a phenomenon that the color purity of the previously obtained pixels is lowered. (Hereinafter, this phenomenon is referred to as “residue color mixing”.)

  Such residual color mixing reduces the color purity of the obtained color filter, and even if a colorant with high color purity and high coloring power is used, the effect is reduced, and a color filter with high color separation is obtained. Couldn't get.

The present invention has been made in view of the above-described situation, and an object thereof is to achieve the following object.
That is, an object of the present invention is to provide a colored radiation-sensitive composition capable of forming a colored cured film in which the occurrence of residual color mixture is suppressed when applied to the formation of a multicolored colored cured film.
Another object of the present invention is to provide a pattern forming method capable of forming a patterned colored cured film in which the occurrence of residual color mixing is suppressed when applied to the formation of a multicolored colored cured film. .
Furthermore, an object of the present invention is to provide a color filter having high color separation and resolution, a method for manufacturing the same, and a solid-state imaging device.

The inventors of the present invention conducted intensive studies in view of the above circumstances, and (A) C.I. I. Pigment Red 254, a colored radiation-sensitive composition containing (B) a binder having a specific structure, (C) a polyfunctional photopolymerizable compound having an alkyleneoxy chain, (D) a photopolymerization initiator, and (E) a solvent. The inventors have found that the above problems can be solved, and have completed the present invention.
Means for solving the above problems are as follows.

<1> At least (A) C.I. I. Pigment red 254, (B) a binder containing 5.0 to 15.0 mol% of a compound represented by the following general formula (1) as a copolymerization component, (C) a polyfunctional photopolymerizable compound having an alkyleneoxy chain, A colored radiation-sensitive composition containing (D) a photopolymerization initiator and (E) an organic solvent.

In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 25 carbon atoms.

<2> The colored radiation-sensitive composition according to <1>, wherein the binder further comprises an aryl (meth) acrylate or an alkyl (meth) acrylate as a copolymerization component.
<3> The colored radiation-sensitive composition according to <1> or <2>, wherein the binder is a binder further containing (meth) acrylic acid as a copolymerization component.
<4> A quaternary system in which the binder has a copolymer component composed of 5.0 to 15.0 mol% of the compound represented by the general formula (1), benzyl methacrylate, methyl methacrylate, and methacrylic acid. The colored radiation-sensitive composition according to any one of <1> to <3>, which is a resin obtained by adding glycidyl methacrylate to a part of a structural unit derived from methacrylic acid in a copolymer.
<5> The colored radiation-sensitive composition according to <4>, wherein the content of the structural unit to which glycidyl methacrylate is added in the binder is 20 to 30 mol%.

< 6 > The polyfunctional photopolymerizable compound having an alkyleneoxy chain includes at least one selected from the group of compounds represented by the following general formula (i) or (ii): <1> to < 5 > The colored radiation-sensitive composition according to any one of the above.

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

< 7 > The colored radiation-sensitive composition according to < 1> to < 6 >, wherein the photopolymerization initiator is an oxime compound.

< 8 > A color filter using the colored radiation-sensitive composition according to any one of <1> to < 7 >.
< 9 > The step of applying the colored radiation-sensitive composition according to any one of <1> to < 7 > onto a support to form a colored radiation-sensitive composition layer, and the colored radiation-sensitive composition. A pattern forming method comprising: exposing a physical layer in a pattern; and developing the colored radiation-sensitive composition layer after exposure to form a colored pattern.
< 10 > A method for producing a color filter including a step of forming a colored pattern on a substrate using the pattern forming method according to < 9 >.
< 11 > A solid-state imaging device comprising the color filter according to < 8 >.

ADVANTAGE OF THE INVENTION According to this invention, when applied to formation of a multicolored colored cured film, the colored radiation-sensitive composition which can form the colored cured film with which generation | occurrence | production of residue color mixture was suppressed can be provided.
In addition, the present invention can provide a pattern forming method capable of forming a patterned colored cured film in which the occurrence of residual color mixture is suppressed when applied to the formation of a multicolored colored cured film.
Furthermore, the present invention can provide a color filter having high color separation and resolution, a manufacturing method thereof, and a solid-state imaging device.

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

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

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

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

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

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

  The colored region in the color filter of the present invention includes a colored pixel (colored pattern) region and a light shielding film forming region in the color filter.

[Colored radiation-sensitive composition]
The colored radiation-sensitive composition of the present invention contains at least (A) C.I. I. Pigment red 254, (B) a binder containing 5.0 to 15.0 mol% of a compound represented by the following general formula (1) as a copolymerization component, (C) a polyfunctional photopolymerizable compound having an alkyleneoxy chain, (D) contains a photopolymerization initiator and (E) an organic solvent.

In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 25 carbon atoms.

The colored radiation-sensitive composition of the present invention contains the components (A) to (E), and when applied to the formation of a multicolored colored cured film, the coloration in which residual color mixing is suppressed is suppressed. A cured film can be formed.
When the colored radiation-sensitive composition of the present invention is used for forming a colored cured film of the first color, it effectively suppresses the occurrence of color mixing of residues, regardless of whether it is used for forming a colored cured film of the next color. be able to.
Hereinafter, each component contained in the colored radiation-sensitive composition of the present invention will be described in detail.

<(A) C.I. I. Pigment Red 254>
The colored radiation-sensitive composition of the present invention contains a pigment as a colorant, and C.I. I. Pigment Red 254 (hereinafter also referred to as “CI Pigment Red 254”, “CIPR 254”, “PR 254”. The same applies to other pigments), and other pigments as necessary. May be.

  In the colored radiation-sensitive composition of the present invention, C.I. I. Pigment Red 25 alone may be contained. I. Pigment red 254 and C.I. I. Other pigments other than CI Pigment Red 254 may be used in combination.

<Other pigments>
The colored radiation-sensitive composition of the present invention includes C.I. I. A known pigment other than CI Pigment Red 254 may be contained.

  C. Applicable to the colored radiation-sensitive composition of the present invention I. As a known pigment other than CI Pigment Red 254, a conventionally known yellow pigment is preferable, and one or more of these yellow pigments can be used. The yellow pigment is appropriately selected according to the use of the colored radiation-sensitive composition.

Examples of the yellow pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 17 , Etc. 176,177,179,180,181,182,185,187,188,193,194,199,213,214.

  Among the yellow pigments described above, C.I. I. Pigment Yellow 139 is more preferable.

  C. I. The mass ratio of CI Pigment Red 254 to the yellow pigment is preferably 100: 5 to 100: 80, and more preferably 100: 10 to 100: 65. In this range, the light transmittance from 400 nm to 500 nm can be suppressed, the color purity can be further improved, and sufficient coloring power can be obtained.

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

The content of the pigment contained in the colored radiation-sensitive composition is preferably 20% by mass to 80% by mass, and 25% by mass to 65% by mass in the total solid content of the colored radiation-sensitive composition. More preferably, 30 mass%-50 mass% is still more preferable.
By setting the pigment content in the above range, an appropriate chromaticity can be obtained when a color filter is produced from the colored radiation-sensitive composition. Further, since radiation curing is sufficiently advanced and the strength as a colored cured film can be maintained, it is possible to prevent the development latitude during alkali development from becoming narrow.

The colored radiation-sensitive composition of the present invention is prepared in advance from (A) C.I. I. Pigment Red 254 is dispersed with a pigment dispersant, an organic solvent, a pigment derivative, and other components as necessary to prepare a pigment dispersion, and the obtained pigment dispersion is represented by (B) general formula (1). A binder containing 5.0 to 15.0 mol% of the compound represented as a copolymerization component, (C) a polymerizable compound having an alkyleneoxy chain, (D) a photopolymerization initiator, and other components added as necessary It is preferable to prepare it by mixing with.
The pigment dispersion can contain a pigment dispersant, a pigment derivative, a polymer material, an organic solvent, and the like as necessary.
The composition of the pigment dispersion and the method for preparing the pigment dispersion are described in detail below.

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

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

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

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

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

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

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

  These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant. In addition, the pigment dispersant in the present invention may be used in combination with an alkali-soluble resin described later together with a terminal-modified polymer, a graft polymer, or a block polymer having an anchor site to the pigment surface. Good.

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

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

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

  As the pigment derivative, quinoline-based, benzimidazolone-based and isoindoline-based pigment derivatives are particularly preferable, and quinoline-based and benzimidazolone-based pigment derivatives are more preferable.

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

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

(Polymer material)
In addition to the above-described components, the pigment dispersion is represented by the general formula (1) from the viewpoints of improving dispersion stability and controlling developability when the pigment dispersion is applied to a colored radiation-sensitive composition. It may further contain a binder containing a compound as a copolymerization component and / or a polymer material having another structure.

The binder containing the compound represented by the general formula (1) as a copolymerization component will be described later. Examples of polymer materials having other structures include polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, and (meth) acrylic materials. Examples thereof include copolymers (particularly (meth) acrylic acid-based copolymers containing a carboxylic acid group and a polymerizable group in the side chain), naphthalenesulfonic acid formalin condensates, and the like. Such a polymer material is adsorbed on the surface of the pigment and acts to prevent re-aggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the pigment surface are used. Preferable examples include a graft copolymer including a monomer containing a heterocyclic ring and a polymerizable oligomer having an ethylenically unsaturated bond as a copolymer unit.
Other polymer materials include polyamidoamine phosphate, high molecular weight unsaturated polycarboxylic acid, polyether ester, aromatic sulfonic acid formalin polycondensate, polyoxyethylene nonyl phenyl ether, polyester amine, polyoxyethylene sorbitan Examples include monooleate polyoxyethylene monostearate.

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

<(B) Binder containing compound represented by general formula (1) as copolymerization component>
The colored radiation-sensitive composition of the present invention comprises (B) a binder containing 5.0 to 15.0 mol% of a compound represented by the following general formula (1) as a copolymerization component (hereinafter referred to as “specific binder” as appropriate). Containing).

In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 25 carbon atoms.

The alkyl group represented by R ¹ and R ² in the general formula (1) may further have a substituent.

The alkyl group having 1 to 25 carbon atoms represented by R ¹ and R ² is not particularly limited. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t- Linear or branched alkyl groups such as amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2 -An alicyclic group such as methyl-2-adamantyl; an alkyl group substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; an alkyl group substituted with an aryl group such as benzyl; and the like. Of these, acids such as methyl, ethyl, cyclohexyl, benzyl, etc., and primary or secondary hydrocarbon groups that are difficult to be removed by heat are particularly preferred in terms of heat resistance.
Note that R ¹ and R ² may be the same type of substituents or different substituents.

Examples of the compound represented by the general formula (1) include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2. -Propenoate, di (n-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2,2'-[oxybis (methylene)] bis-2-propenoate , Di (t-butyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, and the like. It is done.
Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate is particularly preferable.

The specific binder of the present invention may further contain a copolymer component other than the compound represented by the general formula (1).
The copolymer component other than the compound represented by the general formula (1) is not particularly limited, but from the viewpoint of ease of handling such as solubility in an organic solvent, aryl (meth) acrylate and alkyl imparting oil solubility It is preferable that (meth) acrylate and polyethyleneoxy (meth) acrylate are contained as a copolymerization component.
Of these, aryl (meth) acrylate or alkyl (meth) acrylate is preferably included as a copolymerization component.

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

Further, from the viewpoint of alkali developability, monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid containing acidic groups, monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, maleic anhydride and itaconic anhydride It is preferable that a monomer having a carboxylic anhydride group such as an acid is included as a copolymerization component.
Among these, it is preferable to contain (meth) acrylic acid as a copolymerization component.

Furthermore, adding a compound having a radical polymerizable double bond to the binder containing the compound represented by the general formula (1) and a copolymer component other than the compound may cause the specific binder to have radiation sensitivity. Since it can have a group, it is a more preferable embodiment.
The treatment method for adding a compound having a radical polymerizable double bond differs depending on the type of monomer to which the compound having a radical polymerizable double bond can be added. For example, carboxyl such as (meth) acrylic acid or itaconic acid When a monomer having a group is used, an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether and a radical A compound having a polymerizable double bond may be added. When a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride is used, 2-hydroxyethyl (meth) acrylate is used. Add compounds with hydroxyl groups and radical polymerizable double bonds such as When a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or 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.

The most preferable combination as a copolymerization component in the specific binder is that a part of the structure derived from methacrylic acid in the copolymer of the compound represented by the general formula (1), benzyl methacrylate, methyl methacrylate, and methacrylic acid is glycidyl methacrylate. It is a specific binder that reacts and has radiation sensitivity.
Among them, as the specific binder, the compound represented by the general formula (1) is advantageous from the viewpoints of solubility in a solvent and developability, and copolymerizes benzyl methacrylate, methyl methacrylate, and / or methacrylic acid. Particularly preferred is a binder copolymerized as a component.

  The content of the copolymer component of the compound represented by the general formula (1) in the specific binder is 5.0 to 15.0 mol%, preferably 6.0 to 14.0 mol%, more preferably 7 0.0 to 13.0 mol%. By setting it as this range, the inhibitory effect of a residue color mixture can be heightened.

  The copolymer component for imparting oil solubility in the specific binder is preferably contained in the specific binder in an amount of 40 to 70 mol%, more preferably 45 to 60 mol%. In this range, the solubility in a solvent is low. Especially improved.

  It is preferable to contain 1.0-40.0 mol% of the copolymerization component containing the acidic group in a specific binder, and 5.0-30.0 mol% is more preferable. By setting it as this range, the alkali developability of the colored radiation-sensitive composition is improved, and the pattern formability is particularly good.

  Moreover, when making a specific binder contain a radiation sensitive group, as for content of the copolymerization component which has a radiation sensitive group, 20-30 mol% in a specific binder is preferable. By setting it as this range, since the sclerosis | hardenability of a radiation sensitive composition becomes high, the inhibitory effect of a residue color mixture can be improved further.

  The molecular weight of the specific binder is preferably 5000 to 14000 in terms of weight average molecular weight, more preferably 8000 to 13000, and most preferably 9000 to 12000. By setting it as this range, the solubility to a solvent and developability become favorable.

  Here, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene. GPC was measured using HLC-8020GPC (manufactured by Tosoh Corporation), and the columns were measured as TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation).

  Although the example of a specific binder is shown below, it is not limited to these. The number attached to each structural unit is mol%. “Me” represents a methyl group.

  The specific binder can be synthesized according to the method described in JP-A-2004-300204.

  The colored radiation-sensitive composition of the present invention may contain one kind of specific binder or two or more kinds. The specific binder may be partially or wholly added in the preparation of the pigment dispersion described above.

  The content of the specific binder in the colored radiation-sensitive composition of the present invention is preferably 0.1 to 50.0% by mass with respect to the total solid content of the colored radiation-sensitive composition, and is 5.0 to 35.0. The mass% is more preferable. By making it within this range, the effect of the present invention is sufficiently exhibited.

The specific binder is preferably contained in another colored radiation-sensitive composition used in combination with the colored radiation-sensitive composition of the present invention when forming a multicolored colored cured film (colored pattern). When the other colored radiation-sensitive composition contains the specific binder, the residue suppressing effect is further improved.
Other colored radiation-sensitive compositions containing a specific binder are not particularly limited as long as they are colored radiation-sensitive compositions that do not contain PR254 and contain other colorants. As the colored radiation-sensitive composition, for example, a green or blue colored radiation-sensitive composition is preferably exemplified. As an example, C.I. I. A green colored radiation-sensitive composition containing a green pigment such as CI Pigment Green 36 or 7 is preferable.

<(C) Polyfunctional photopolymerizable compound having alkyleneoxy chain>
The colored radiation-sensitive composition of the present invention contains (C) at least one polyfunctional photopolymerizable compound having an alkyleneoxy chain.

  In the present invention, the polyfunctional photopolymerizable compound means a photocurable compound having two or more photocurable functional groups. Hereinafter, “(D) a polyfunctional photopolymerizable compound having an alkyleneoxy chain” in the present invention may be referred to as a “specific polymerizable compound” as appropriate.

  The colored radiation-sensitive composition of the present invention can enhance the curability of the colored radiation-sensitive composition by including a specific polymerizable compound, and the pattern forming property in development is improved and the effect of inhibiting the occurrence of residual color mixing is improved. Is further increased.

  As the form of the specific polymerizable compound, (D-1) a polyfunctional photopolymerizable compound having one or more alkyleneoxy chains (hereinafter also referred to as “AO chain”) and having no acidic functional group, (D -2) There are two forms of a polyfunctional photopolymerizable compound having one or more acidic functional groups and one or more AO chains. When the specific polymerizable compound further contains an acidic functional group, the effect of the present invention can be further enhanced.

  When two or more specific polymerizable compounds are contained in the colored radiation-sensitive composition of the present invention, one form is selected when two or more kinds are selected from the two forms (D-1) and (D-2). You may select 2 or more types from the group which consists of, and may select 2 or more types from the group obtained by combining different forms.

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

  The specific polymerizable compound has increased crosslink density due to the photocurable functional group of the compound, and the hydrophilicity is improved by the alkyleneoxy chain of the compound, so that the solubility in an aqueous alkaline developer is also improved. Therefore, in a colored radiation-sensitive composition, a specific polymerizable compound having an alkyleneoxy chain is added even if the amount of a component that does not have curing reactivity and is not alkali-soluble, such as a pigment or a photopolymerization initiator, is increased. As a result, the crosslink density and alkali solubility are improved, so that excellent curability and alkali developability can be obtained.

  When the specific polymerizable compound has an acidic functional group, the acidic functional group only needs to be capable of alkali development, and examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. From the viewpoint of handleability of the colored radiation-sensitive composition, a carboxyl group is preferred.

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

In order to increase the crosslinking density, it is preferable that the specific polymerizable compound has a larger number of photocurable functional groups. From the viewpoint of the crosslinking density, the number of photocurable functional groups in the specific polymerizable compound is preferably 3 or more, more preferably 3 to 30, and particularly preferably 3 to 15.
Further, from the viewpoint of the crosslinking density, the number of photocurable functional groups in the specific polymerizable compound having an acidic functional group is preferably 3 or more.

  Among the specific polymerizable compounds, a pentaerythritol derivative and / or a dipentaerythritol derivative is preferable from the viewpoint of obtaining the effect of the present invention more effectively.

  When the specific polymerizable compound has an acidic functional group, as the specific polymerizable compound, (1) by modifying a monomer or oligomer having three or more photocurable functional groups together with a hydroxyl group with a dibasic acid anhydride Those having a carboxyl group introduced, or (2) those having a sulfonic acid group introduced by modifying an aromatic compound having three or more photocurable functional groups with concentrated sulfuric acid or fuming sulfuric acid can be used. Moreover, you may use the oligomer which contains the monomer which is specific polymerizable compound itself as a repeating unit as a specific polymerizable compound.

  The specific polymerizable compound in the present invention is preferably at least one selected from the group of compounds represented by the following formula (1) or formula (2). Note that at least one T in the formula (1) needs to be an alkyleneoxy chain, and the alkyleneoxy chain is bonded to R or X at the terminal on the carbon atom side. At least one G in the formula (2) needs to be an alkyleneoxy chain, and the alkyleneoxy chain is bonded to W at the carbon atom side end.

In formula (1), n is 0-14 and m is 1-8. In Formula (2), W is R or X similar to Formula (1), and 3 or more Ws are R among 6 Ws. p is 0-14 and q is 1-8. A plurality of R, X, T, and G present in one molecule may be the same or different.
Among the compounds represented by the formulas (1) and (2), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.

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

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

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

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

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

Among the compounds represented by the general formulas (i) and (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferred.

  In particular, as the specific polymerizable compound, the exemplified compound (b) is effective, and the effect of the present invention can be remarkably improved.

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

  Moreover, you may further mix | blend the other photopolymerizable compound which has a 2 or more photopolymerizable functional group with the specific radiation-sensitive composition in the colored radiation sensitive composition of this invention. The specific polymerizable compound increases both the crosslink density and alkali solubility, whereas the above-mentioned “other photopolymerizable compound having two or more photopolymerizable functional groups” increases only the crosslink density. By combining, the crosslinking density and alkali solubility can be adjusted.

Examples of the “other photocurable compound having two or more photopolymerizable functional groups” include simple substances such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate. Functional acrylates and methacrylates; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) ) Polyfunctional alcohols such as isocyanurate, glycerin and trimethylolethane, which are added with ethylene oxide or propylene oxide and then (meth) acrylated, Japanese Patent Publication Nos. 48-41708, 50-6034, Japanese Patent Publication No. Urethane acrylates as described in each publication such as 51-37193, polyesters described in each publication such as JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, etc. Examples thereof include polyfunctional acrylates and methacrylates such as acrylates and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid.
Furthermore, Japan Adhesion Association Vol. 20, No. 7 (pages 300 to 308), which are introduced as photocurable monomers and oligomers, can also be used.

  As content of the specific polymeric compound in the radiation sensitive composition of this invention, 2-50 mass% is preferable with respect to the total solid of this composition, 2-30 mass% is more preferable, Furthermore, 2-20 mass% is more preferable.

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

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

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

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

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

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

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

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

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

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

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

  Further, as oxime compounds other than the above, compounds described in JP-T 2009-519904, in which oxime is linked to the N-position of carbazole, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, and dyes Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292209, in which a nitro group is introduced, and ketoxime compounds described in International Patent Publication No. 2009-131189, triazine skeleton and oxime skeleton are the same molecule A compound described in U.S. Pat. No. 7,556,910 and a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source may be used.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  As the polymerization initiator (D) used in the colored radiation-sensitive composition of the present invention, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine Compound, phosphine oxide compound, metallocene compound, oxime compound, triallylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivative thereof, cyclopentadiene-benzene-iron complex and salt thereof, halomethyloxadiazole Compounds selected from the group consisting of compounds and 3-aryl substituted coumarin compounds are preferred.

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

  In particular, when the colored radiation-sensitive composition of the present invention is used for production of a color filter provided in a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is important that the film is developed without residue. From such a viewpoint, it is particularly preferable to use an oxime compound as the polymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and it is necessary to keep the addition amount of a polymerization initiator low. Considering these points, it is most preferable to use an oxime compound as the polymerization initiator (D) in order to form a fine pattern such as a solid-state imaging device.

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

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

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

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

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

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

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

<Alkali-soluble resin>
The colored radiation-sensitive composition of the present invention preferably further contains an alkali-soluble resin. By containing an alkali-soluble resin, developability and pattern formation are improved.

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

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

  As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolak resins, etc., acid cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group. Can be mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macro Examples of N-substituted maleimide monomers described in JP-A-10-300922 such as monomers and polymethylmethacrylate macromonomers include N-phenylmaleimide and N-cyclohexylmaleimide. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

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

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

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

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

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

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and most preferably 70 to 120 mgKOH / g.
Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 20,000.

  As content in the coloring radiation sensitive composition of alkali-soluble resin, 1-15 mass% is preferable with respect to the total solid of this composition, More preferably, it is 2-12 mass%, Most preferably Is 3-10 mass%. However, it is preferable that it is 50 mass% or less with respect to content of the specific binder in this invention.

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

<Dye>
In the present invention, a dye can be used in combination with a pigment in order to obtain a desired spectrum.
Examples of the dye include pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine , Xanthene-based, phthalocyanine-based, benzopyran-based, pyromethene-based and indigo-based dyes can be used. Specifically, known dyes conventionally used for color filter applications, such as JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-94301, are disclosed. No. 11614, No. 2592207, U.S. Pat. No. 4,808,501, U.S. Pat. No. 5,667,920, U.S. Pat. No. 5,059,500, JP-A-5-333207. JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, JP-A-8-2111599, JP-A-4-249549, JP-A-10-123316. JP-A-11-302283, JP-A-7-286107, JP-A-2001-4823, JP-A-8-15522, JP-A-8-2. 771, JP-A-8-146215, JP-A-11-343437, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222 The dyes described in JP-A No. 2002-14223, JP-A No. 8-302224, JP-A No. 8-73758, JP-A No. 8-179120, JP-A No. 8-151531, and the like are preferable. The toning may be performed when the pigment is dispersed or when the colored radiation-sensitive composition is prepared. The dye may be a multimer.

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

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

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

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

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

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

Specific examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol dilaurate. Stearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, manufactured by BASF, Tetronic 304, 701, 704, 901, 904, 150R1, Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.) ) And the like.
Further, specific examples of the nonionic surfactant include “Pionin D-6112-W”, “Pionin D-6315”, “Pionin D-6512”, and the like manufactured by Takemoto Yushi Co., Ltd.

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

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

Examples of the silicone-based surfactant include “Tore Silicone DC3PA”, “Tore Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, and “Tore Silicone SH29PA” manufactured by Torre Silicone Co., Ltd. , “Tole Silicone SH30PA”, “Tole Silicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-444 (4) (5) (6)” manufactured by Toshiba Silicone Co., Ltd. 7) “6”, “TSF-4460”, “TSF-4452”, “KP341” manufactured by Silicone Corporation, “BYK323”, “BYK330” manufactured by Big Chemie, and the like.
Only one type of surfactant may be used, or two or more types may be combined.

<Organic carboxylic acid, organic carboxylic anhydride>
The colored radiation-sensitive composition of the present invention may contain an organic carboxylic acid having a molecular weight of 1000 or less and / or an organic carboxylic acid anhydride.

  Specific examples of the organic carboxylic acid compound include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, methacrylic acid, oxalic acid, malonic acid, succinic acid, Examples thereof include dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, and tricarboxylic acids such as tricarbaric acid and aconitic acid. Examples of the aromatic carboxylic acid include carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and carboxylic acids in which a carboxyl group is bonded to the phenyl group through a carbon bond. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically maleic acid, malonic acid, succinic acid, and itaconic acid are preferred.

  Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specific examples include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, and tetrahydrophthalic anhydride. Succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. An aliphatic carboxylic acid anhydride is mentioned. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferable.

The addition amount of these organic carboxylic acids and / or organic carboxylic acid anhydrides is generally 0.01 to 10% by mass, preferably 0.03 to 5% by mass, based on the total solid content of the colored radiation-sensitive composition. Preferably it is the range of 0.05-3 mass%.
By adding these organic carboxylic acids and / or organic carboxylic acid anhydrides having a molecular weight of 1000 or less, it is possible to further reduce the remaining undissolved matter of the colored radiation-sensitive composition while maintaining high pattern adhesion. Is possible.

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

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

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

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

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

  The pigment concentration in the colored radiation-sensitive composition of the present invention is the total solid content of the colored radiation-sensitive composition (that is, pigment, dispersant, binder, polymerizable compound, photopolymerizable initiator, and other additives). 40% by mass or more, and more preferably 45% by mass or more, based on the total mass of the components excluding the solvent.

[Pattern Forming Method, Color Filter and Manufacturing Method Thereof]
Next, a pattern forming method, a color filter, and a manufacturing method thereof according to the present invention will be described.
The pattern forming method of the present invention includes a step of forming a radiation-sensitive composition layer (colored layer) by applying the radiation-sensitive composition of the present invention on a support (colored layer forming step), and the radiation-sensitive composition. A step of exposing the photosensitive composition layer in a pattern (exposure step) and a step of developing the radiation-sensitive composition layer after exposure to form a colored pattern (development step). .

The pattern forming method of the present invention uses the radiation-sensitive composition of the present invention for forming a colored pattern on a support, and even when applied to the formation of a multicolored colored pattern (colored cured film). Occurrence of residual color mixture is effectively suppressed.
The pattern forming method of the present invention can be applied to formation of a colored pattern possessed by a color filter, and is particularly suitable for forming a colored pattern possessed by a color filter.

  The support for forming a colored pattern by the pattern forming method of the present invention is not particularly limited as long as it is a support applicable to the formation of a colored pattern in addition to a plate-like material such as a substrate.

  Each step such as the colored layer forming step, the exposure step, and the developing step in the pattern forming method of the present invention will be described in detail below through the method for producing a color filter of the present invention.

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

The manufacturing method of the color filter of this invention has the process of forming a colored pattern on a board | substrate, applying the pattern formation method of this invention.
That is, a method for producing a color filter of the present invention, a step of applying the radiation-sensitive composition of the present invention on a substrate to form a radiation-sensitive composition layer (colored layer) (colored layer forming step), and the above-mentioned sensitivity It includes a step of exposing the radiation-sensitive composition layer in a pattern (exposure step) and a step of developing the radiation-sensitive composition layer after exposure to form a colored pattern (development step). .

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

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

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

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

  The coating thickness of the colored layer after drying (hereinafter referred to as “dry thickness” as appropriate) is as follows. From the viewpoint of ensuring color density, light in an oblique direction does not reach the light receiving portion, and the edge and center of the device. From the viewpoint of reducing problems such as a significant difference in the light collection rate, it is preferably 0.05 μm or more and less than 2.0 μm, more preferably 0.1 μm or more and 1.5 μm or less, and 0.2 μm or more and 1.0 μm. The following are particularly preferred:

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

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

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

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

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

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

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

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

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

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

(Binder synthesis example)
Binders 1 to 6 used in Examples and Comparative Examples were synthesized as follows. Binders 1 to 4 are specific binders, and binders 5 and 6 are comparative binders.

(Synthesis of binder 1)
A solution having the following composition was prepared in a monomer dropping container.
・ Dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (hereinafter referred to as “DM”) 20 parts ・ Benzyl methacrylate (hereinafter referred to as “BzMA”) 70 parts ・ Methyl methacrylate (Hereinafter referred to as “MMA”) 10 parts methacrylic acid (hereinafter referred to as “MAA”) 30 parts t-butyl peroxy-2-ethylhexanoate 2 parts diethylene glycol dimethyl ether 25 parts

A solution having the following composition was prepared in a container for dropping a chain transfer agent.
・ 6 parts of n-dodecanethiol ・ 20 parts of diethylene glycol dimethyl ether

157 parts of diethylene glycol dimethyl ether was added to the reaction vessel (separable flask with a cooling tube), and after replacing with N ₂ gas, the temperature of the reaction vessel was raised to 90 ° C. by heating.
After confirming the temperature stability, the dropping of the monomer and the chain transfer agent was started from the monomer dropping vessel and the chain transfer agent dropping vessel, respectively, and the dropping of the monomer and the chain transfer agent was completed in 140 minutes while maintaining the temperature of 90 ° C. 60 minutes after the completion of dropping, the temperature was further raised, the temperature of the reaction vessel was raised to 110 ° C., and the temperature was maintained at 110 ° C. for 180 minutes. Thereafter, the inside of the reaction vessel was replaced with air.

Next, a composition having the following composition was charged into the reaction vessel and reacted for 9 hours at a temperature of 110 ° C.
・ Glycidyl methacrylate (hereinafter referred to as “GMA”) 35 parts ・ 2,2′-methylenebis (4-methyl-6-tert-butylphenol) 0.2 part ・ Triethylamine 0.4 part After reaction, cool to room temperature did.
In this way, a solution of binder 1 (solid content concentration 40%) was obtained.
The component derived from each monomer of the obtained binder 1 was analyzed using ¹ H-NMR. The weight molecular weight was measured by GPC.

(Synthesis of binder 2)
A solution having the following composition was prepared in a monomer dropping container.
DM 22 parts BzMA 70 parts MMA 20 parts MAA 50 parts t-butyl peroxy-2-ethylhexanoate 2 parts diethylene glycol dimethyl ether 32 parts

A solution having the following composition was prepared in a container for dropping a chain transfer agent.
・ 7 parts of n-dodecanethiol ・ 20 parts of diethylene glycol dimethyl ether 188 parts of diethylene glycol dimethyl ether was added to the reaction vessel (separable flask with cooling tube), and after replacing with N ₂ gas, the temperature of the reaction vessel was raised to 90 ° C. by heating. .
After confirming temperature stability, dripping was started from the monomer dropping container and the chain transfer agent dropping container, and dropping of the monomer and the chain transfer agent was completed in 140 minutes while maintaining the temperature of 90 ° C.
60 minutes after the completion of dropping, the temperature was further raised, the temperature of the reaction vessel was raised to 110 ° C., and the temperature was maintained at 110 ° C. for 180 minutes. Thereafter, the inside of the reaction vessel was replaced with air.

Next, a composition having the following composition was charged into the reaction vessel and reacted for 9 hours at a temperature of 110 ° C.
GMA 40 parts 2,2′-methylenebis (4-methyl-6-tert-butylphenol) 0.2 part Triethylamine 0.4 part After completion of the reaction, 62 parts of diethylene glycol dimethyl ether was added and cooled to room temperature.
In this way, a solution of binder 2 (solid content concentration 40%) was obtained.
It was also analyzed by ^{1 H-NMR} for the components from each raw material monomer of the resulting binder 2. The weight molecular weight was measured by GPC.

(Synthesis of binder 3)
A solution having the following composition was prepared in a monomer dropping container.
DM 12 parts BzMA 70 parts MMA 10 parts MAA 30 parts t-butyl peroxy-2-ethylhexanoate 2 parts diethylene glycol dimethyl ether 34 parts

A solution having the following contents was prepared in a container for dropping a chain transfer agent.
・ 6 parts of n-dodecanethiol ・ 20 parts of diethylene glycol dimethyl ether 188 parts of diethylene glycol dimethyl ether was added to a reaction vessel (separable flask with a cooling tube), replaced with N ₂ gas, and heated to raise the temperature of the reaction vessel to 90 ° C. .
After confirming temperature stability, dripping was started from the monomer dropping container and the chain transfer agent dropping container, and dropping of the monomer and the chain transfer agent was completed in 140 minutes while maintaining the temperature of 90 ° C.
60 minutes after the completion of dropping, the temperature was further raised, the temperature of the reaction vessel was raised to 110 ° C., and the temperature was maintained at 110 ° C. for 180 minutes. Thereafter, the inside of the reaction vessel was replaced with air.
Next, a composition having the following composition was charged into the reaction vessel and reacted for 9 hours at a temperature of 110 ° C.
・ 35 parts of GMA ・ 0.2 part of 2,2′-methylenebis (4-methyl-6-tert-butylphenol) ・ 0.4 part of triethylamine

After completion of the reaction, 39 parts of diethylene glycol dimethyl ether was added and cooled to room temperature.
In this way, a solution of binder 3 (solid content concentration 40%) was obtained.
It was also analyzed by ^{1 H-NMR} for the components from each raw material monomer of the resulting binder 3. The weight molecular weight was measured by GPC.

(Synthesis of binder 4)
A solution having the following composition was prepared in a monomer dropping container.
DM 30 parts BzMA 70 parts MMA 10 parts MAA 30 parts t-butylperoxy-2-ethylhexanoate 2 parts diethylene glycol dimethyl ether 36 parts

A solution having the following contents was prepared in a container for dropping a chain transfer agent.
-5 parts of n-dodecanethiol-20 parts of diethylene glycol dimethyl ether 188 parts of diethylene glycol dimethyl ether were added to a reaction vessel (separable flask with a cooling tube), replaced with N ₂ gas, and heated to raise the temperature of the reaction vessel to 90 ° C. .
After confirming temperature stability, dripping was started from the monomer dropping container and the chain transfer agent dropping container, and dropping of the monomer and the chain transfer agent was completed in 140 minutes while maintaining the temperature of 90 ° C.
60 minutes after the completion of dropping, the temperature was further raised, the temperature of the reaction vessel was raised to 110 ° C., and the temperature was maintained at 110 ° C. for 180 minutes. Thereafter, the inside of the reaction vessel was replaced with air.
Next, a composition having the following composition was charged into the reaction vessel and reacted for 9 hours at a temperature of 110 ° C.
-35 parts of GMA-0.2 part of 2,2'-methylenebis (4-methyl-6-t-butylphenol)-0.4 part of triethylamine After completion of the reaction, 18 parts of diethylene glycol dimethyl ether was added and cooled to room temperature.
In this way, a solution of binder 4 (solid content concentration 40%) was obtained.
It was also analyzed by ^{1 H-NMR} for the components from each raw material monomer of the resulting binder 4. The weight molecular weight was measured by GPC.

(Synthesis of binder 5)
A solution having the following composition was prepared in a monomer dropping container.
・ BzMA 70 parts ・ MMA 10 parts ・ MAA 30 parts ・ t-butylperoxy-2-ethylhexanoate 2 parts ・ Diethylene glycol dimethyl ether 32 parts

A solution having the following composition was prepared in a container for dropping a chain transfer agent.
・ 6 parts of n-dodecanethiol ・ 20 parts of diethylene glycol dimethyl ether 188 parts of diethylene glycol dimethyl ether was added to a reaction vessel (separable flask with a cooling tube), replaced with N ₂ gas, and heated to raise the temperature of the reaction vessel to 90 ° C. .
After confirming temperature stability, dripping was started from the monomer dropping container and the chain transfer agent dropping container, and dropping of the monomer and the chain transfer agent was completed in 140 minutes while maintaining the temperature of 90 ° C.
60 minutes after the completion of dropping, the temperature was further raised, the temperature of the reaction vessel was raised to 110 ° C., and the temperature was maintained at 110 ° C. for 180 minutes. Thereafter, the inside of the reaction vessel was replaced with air.

Next, a composition having the following composition was charged into the reaction vessel and reacted for 9 hours at a temperature of 110 ° C.
-35 parts of GMA-0.2 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol)-0.4 parts of triethylamine After completion of the reaction, 62 parts of diethylene glycol dimethyl ether was added and cooled to room temperature.
In this way, a solution of binder 2 (solid content concentration 40%) was obtained.
It was also analyzed by ^{1 H-NMR} for the components from each raw material monomer of the resulting binder 2. The weight molecular weight was measured by GPC.

(Synthesis of binder 6)
A solution having the following composition was prepared in a monomer dropping container.
DM 40 parts BzMA 70 parts MMA 10 parts MAA 30 parts t-butylperoxy-2-ethylhexanoate 2 parts diethylene glycol dimethyl ether 32 parts

A solution having the following composition was prepared in a container for dropping a chain transfer agent.
・ 6 parts of n-dodecanethiol ・ 20 parts of diethylene glycol dimethyl ether 188 parts of diethylene glycol dimethyl ether was added to a reaction vessel (separable flask with a cooling tube), replaced with N ₂ gas, and heated to raise the temperature of the reaction vessel to 90 ° C. .
After confirming temperature stability, dripping was started from the monomer dropping container and the chain transfer agent dropping container, and dropping of the monomer and the chain transfer agent was completed in 140 minutes while maintaining the temperature of 90 ° C.
60 minutes after the completion of dropping, the temperature was further raised, the temperature of the reaction vessel was raised to 110 ° C., and the temperature was maintained at 110 ° C. for 180 minutes. Thereafter, the inside of the reaction vessel was replaced with air.

Next, a composition having the following composition was charged into the reaction vessel and reacted for 9 hours at a temperature of 110 ° C.
-35 parts of GMA-0.2 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol)-0.4 parts of triethylamine After completion of the reaction, 62 parts of diethylene glycol dimethyl ether was added and cooled to room temperature.
In this way, a solution of binder 2 (solid content concentration 40%) was obtained.
It was also analyzed by ^{1 H-NMR} for the components from each raw material monomer of the resulting binder 2. The weight molecular weight was measured by GPC.

  Table 1 summarizes the composition (mol%) of the components derived from the monomers of the binders 1 to 6 obtained above and the weight average molecular weight of the binder. “GMA” in Table 1 represents the composition ratio (mol%) of the structure in which GMA is added to the structural unit derived from “MAA”.

(Preparation of pigment dispersion)
(Pigment dispersion 1: Preparation of dispersion containing PR254 / PY139)
9.6 parts of Pigment Red 254, 4.3 parts of Pigment Yellow 139, 6.8 parts of pigment dispersant BYK-161 (manufactured by BYK), propylene glycol methyl ether acetate (hereinafter referred to as “PGMEA”). A mixed liquid consisting of 79.3 parts was mixed and dispersed for 3 hours by a bead mill (zirconia beads 0.3 mm diameter) to prepare a pigment dispersion. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.).
This dispersion treatment was repeated 10 times to obtain a pigment dispersion 1.

(Pigment dispersion 2: Dispersion containing PG36 / PG7 / PY139)
Pigment Green 36, 5.9 parts, Pigment Green 7 5.5 parts, Pigment Yellow 139 5.1 parts, pigment dispersant BYK-161 (manufactured by BYK) 8.1 parts, and PGMEA 75.4 parts. The mixed solution was mixed and dispersed for 3 hours by a bead mill (zirconia beads 0.3 mm diameter) to prepare a pigment dispersion. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.).
This dispersion treatment was repeated 10 times to obtain a pigment dispersion 2.

(Pigment dispersion 3: Dispersion containing PB15: 6 / PV23)
Pigment Blue 15: 6, 9.5 parts, Pigment Violet 23, 2.4 parts, pigment dispersant BYK-161 (manufactured by BYK) 5.6 parts, and PGMEA 82.5 parts were mixed with a bead mill (zirconia). A pigment dispersion was prepared by mixing and dispersing for 3 hours using beads having a diameter of 0.3 mm. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.).
This dispersion treatment was repeated 10 times to obtain a pigment dispersion 3.

(Preparation of colored radiation-sensitive composition)
Example 1
(Preparation of colored radiation-sensitive composition Red-1)
Using the pigment dispersion 1 obtained above, each component was mixed and stirred so as to have the following composition to prepare a red colored radiation-sensitive composition Red-1 of Example 1.
<Composition>
(A) Pigment dispersion: 69.74 parts of Pigment dispersion 1 (B) Specific binder: 8.60 parts of binder 1 obtained in the above synthesis example (C) Specific polymerizable compound: Polymerizable compound A (below Structure) 3.41 parts ・ (D) Photopolymerization initiator: IRGACURE OXE-01 (the following structure, manufactured by BASF) 0.98 parts ・ Surfactant:
Megafuck F-781 (manufactured by DIC Corporation, 0.2% 3-ethoxypropionate ethyl solution) 4.17 parts Pionein D-6112-W (manufactured by Takemoto Yushi Co., Ltd.) 1.68 parts, polymerization inhibitor : P-methoxyphenol (1.0% PGMEA solution) 0.002 part (E) Organic solvent:
PGMEA 4.17 parts ethyl 3-ethoxypropionate (hereinafter referred to as “EEP”) 7.24 parts

(Examples 2-6 and Comparative Examples 1-8)
(Preparation of colored radiation-sensitive compositions Red-2 to Red-6, Red-7 to Red-14)
In the preparation of the colored radiation-sensitive composition Red-1 of Example 1, instead of the binder 1 as the specific binder and the polymerizable compound A as the specific polymerizable compound, the types of binders listed in Table 2 and Except for using the polymerizable compound, the colored radiation-sensitive compositions Red-2 to Red-6 and Red-7 to Red-- of Examples 2 to 6 and Comparative Examples 1 to 8 were the same as Example 1. 14 was prepared.

(Preparation of green radiation-sensitive composition)
Using the pigment dispersion 2 obtained above, each component was mixed and stirred so as to have the following composition to prepare a green radiation-sensitive composition.
<Composition>
Pigment dispersion: 58.90 parts of pigment dispersion 2 Binder: 11.01 parts of binder 1 obtained in the above synthesis example Polymerizable compound:
Dipentaerythritol hexaacrylate (hereinafter referred to as DPHA) (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 5.48 parts Polymerizable compound B (structure below) 3.66 parts Photopolymerization initiator: IRGACURE OXE- 01 (the following structure, manufactured by BASF) 2.19 parts-Surfactant:
Megafuck F-781 (manufactured by DIC Corporation, 0.2% PGMEA solution) 4.17 parts Pionein D-6315 (manufactured by Takemoto Yushi Co., Ltd.) 0.33 parts Polymerization inhibitor: p-methoxyphenol (1 0.00% PGMEA solution) 0.005 part Organic solvent: PGMEA 4.25 parts

(Preparation of blue radiation-sensitive composition)
Using the pigment dispersion 3 obtained above, each component was mixed and stirred to obtain the following composition to prepare a blue radiation-sensitive composition.
<Composition>
Pigment dispersion: 48.32 parts of pigment dispersion 3Binder:
Binder A (the following structure, 39% PGMEA solution) 6.31 parts Binder B (the following structure, 54% PGMEA solution) 2.30 parts Polymerizable compound:
DPHA (manufactured by Nippon Kayaku Co., Ltd.) 3.83 parts polymerizable compound B (structure shown below) 3.83 parts / photopolymerization initiator: IRGACURE OXE-01 (structure shown below, manufactured by BASF) 2.95 parts / interface Activator:
Megafuck F-781 (manufactured by DIC Corporation, 0.2% EEP solution) 4.17 parts Pionein D-6112-W (manufactured by Takemoto Yushi Co., Ltd.) 0.23 parts Polymerization inhibitor: p-methoxyphenol (1.0% PGMEA solution) 0.004 parts Organic solvent: EEP 28.05 parts

Each component used in the examples and comparative examples is shown below.

[Evaluation]
Using the colored radiation-sensitive compositions Red-1 to Red-14, the green radiation-sensitive composition, and the blue radiation-sensitive composition of Examples 1 to 6 and Comparative Examples 1 to 8 obtained above. The residue color mixture was evaluated.

<Preparation of glass wafer with undercoat layer>
A glass wafer with an undercoat layer used for evaluation was produced as follows.

(1) Preparation of composition for undercoat layer • Propylene glycol monomethyl ether acetate (PGMEA) 19.20 parts • Ethyl lactate 36.67 parts • Binder: (benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate) Polymer (molar ratio = 60: 20: 20) 41% EL solution 30.51 parts ・ Dipentaerythritol hexaacrylate 12.20 parts ・ Polymerization inhibitor (p-methoxyphenol) 0.006 parts ・ Fluorosurfactant 0.83 parts, photopolymerization initiator TAZ-107 (manufactured by Midori Chemical Co., Ltd.) 0.59 parts

(2) Production of glass wafer with undercoat layer On the 8-inch glass wafer, the composition for undercoat layer obtained above was uniformly applied by spin coating to form a coating film, and the formed coating film was formed at 120 ° C. It heat-processed for 120 second on the hotplate. The spin coating speed was adjusted so that the thickness of the coating film after the heat treatment was about 0.5 μm.
The coating film after the heat treatment was further treated in an oven at 220 ° C. for 1 hour to cure the coating film to form an undercoat layer.
As described above, a glass wafer with an undercoat layer in which an undercoat layer was formed on an 8-inch glass wafer was obtained.

<Evaluation of residual color mixture>
The evaluation of the residual color mixture was performed using 56 combinations of colored radiation-sensitive compositions described in Tables 3 and 4 below. Details are as follows. The evaluation results are shown in Tables 3 and 4.

The colored radiation-sensitive composition used for forming the first colored pattern of the color filter was applied onto a glass wafer with an undercoat layer using a spin coater so that the film thickness after drying was 1.0 μm, and 100 ° C. A heat treatment (pre-baking) was performed for 120 seconds using a hot plate.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Co., Ltd.), 365 nm wavelength light was exposed at 1000 mJ / cm ² through a mask having a 2 cm × 2 cm pattern.
Then, the glass wafer on which the exposed coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (Fuji Film Electronics Co., Ltd.). Paddle development was performed at 23 ° C. for 60 seconds using a 60% diluted solution (manufactured by Materials Co., Ltd.) to form a colored pattern on the glass wafer.
A glass wafer on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the glass wafer is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is ejected from above the rotation center from a jet nozzle. And rinsed, and then spray-dried.
Furthermore, heat treatment (post-baking) was performed for 480 seconds using a 200 ° C. hot plate to obtain a monochromatic color filter on which a first color pattern was formed.

A spin coater is used on the obtained monochromatic color filter having the coloring pattern of the first layer so that the colored radiation-sensitive composition having a color different from that of the first layer is 1.0 μm after drying. Then, a heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C., and a second colored radiation-sensitive composition layer (second layer) was formed on the first color filter. A laminated color filter was obtained.
Next, the obtained laminated color filter was subjected to development, rinsing and drying in the same manner as the formation of the first colored pixel, and the colored radiation-sensitive composition layer in the uncured part was developed and removed.

Spectral variation (ΔT% max) of maximum transmittance after the production of a single color filter in which the colored pixels of the first layer are formed and after the development removal of the second layer is expressed as MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). The residual color mixture of the second layer of the colored radiation-sensitive composition remaining on the colored pixel formed as the first layer was evaluated. The smaller the variation, the more difficult the color mixing of the residue, which is more desirable.
~ Criteria ~
A: ΔT% max <0.5%
○: 0.5% <ΔT% max <1.0%
Δ: 1.0% <ΔT% max <3.0%
×: 3.0% <ΔT% max
In the above judgment criteria, ◎ or ○ is a level that does not cause any practical problem.

  As shown in Table 3 and Table 4, it can be seen that the color mixing of the residue is suppressed by using the colored radiation-sensitive composition of the example for forming the colored pattern of the first layer or the second layer.

(Example 7: Production of color filter for solid-state imaging device)
<Preparation of silicon wafer with undercoat layer>
The undercoat layer composition was uniformly applied on an 8-inch silicon wafer by spin coating to form a coating film, and the formed coating film was heat-treated on a hot plate at 120 ° C. for 120 seconds. The spin coating speed was adjusted so that the thickness of the coating film after the heat treatment was about 0.5 μm.
The coating film after the heat treatment was further treated in an oven at 220 ° C. for 1 hour to cure the coating film to form an undercoat layer.
As described above, a silicon wafer with an undercoat layer in which an undercoat layer was formed on an 8-inch silicon wafer was obtained.

<Preparation of color filter for solid-state image sensor>
On the undercoat layer of the silicon wafer with the undercoat layer, the red colored radiation-sensitive composition prepared in Examples 1 and 2 was applied so that the dry thickness of each coating film was 1.0 μm. A curable coating film was formed. And the heat processing (prebaking) for 120 second was performed with respect to the board | substrate after coating film formation using a 100 degreeC hotplate. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Co., Ltd.), light having a wavelength of 365 nm is passed through an island pattern mask having a pattern of 3.0 μm square to 100 mJ / cm ^{2 to} 2500 mJ / cm ^2. Irradiation was performed while changing the exposure amount by 100 mJ / cm ^{2 in} the range of. Thereafter, the silicon wafer on which the coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type; manufactured by Chemitronics), and CD-2000 (Fuji Film Electronics Materials ( The product was subjected to paddle development at 23 ° C. for 60 seconds to form a red colored pattern on the silicon wafer substrate.

  A silicon wafer on which a red colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and pure water is spouted from an upper part of the rotation center of the silicon wafer while rotating the silicon wafer at a rotation speed of 50 rpm. A rinse treatment was performed by supplying in a shower form, and then spray drying was performed to obtain a color filter.

  The formed red coloring pattern was observed with a length measurement SEM S-9260A (manufactured by Hitachi High-Technologies Corporation) and a cross-section SEM S-4800 (manufactured by Hitachi High-Technologies Corporation). Shows a good rectangular profile, and was found to be a color filter suitable for a solid-state imaging device.

  From this, according to the colored radiation-sensitive composition of the present invention, it is possible to provide a color filter having an excellent pattern shape without changing the spectrum of the red pixel portion and the adjacent pixel portion.

Claims (11)

At least (A) C.I. I. Pigment Red 254, (B) a binder containing a compound represented by the following general formula (1) as a copolymerization component in the range of 5.0 to 15.0 mol%, and (C) a polyfunctional photopolymerization having an alkyleneoxy chain. A colored radiation-sensitive composition containing a reactive compound, (D) a photopolymerization initiator, and (E) an organic solvent.


(In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 25 carbon atoms.)   The colored radiation-sensitive composition according to claim 1, wherein the binder further comprises an aryl (meth) acrylate or an alkyl (meth) acrylate as a copolymerization component.   The colored radiation-sensitive composition according to claim 1, wherein the binder is a binder further containing (meth) acrylic acid as a copolymerization component.   The binder is a quaternary copolymer having a copolymer component composed of 5.0 to 15.0 mol% of the compound represented by the general formula (1), benzyl methacrylate, methyl methacrylate, and methacrylic acid. The colored radiation-sensitive composition according to any one of claims 1 to 3, which is a resin obtained by adding glycidyl methacrylate to a part of a structural unit derived from methacrylic acid.   The colored radiation-sensitive composition according to claim 4, wherein the content of the structural unit to which glycidyl methacrylate is added in the binder is 20 to 30 mol%. Polyfunctional photopolymerizable compound having an alkyleneoxy chain, any one of claims 1 to 5 comprising at least one member selected from the group of compounds represented by the following general formula (i) or (ii) 1 The colored radiation-sensitive composition according to item.


(In the general formula (i) or (ii), E are each _{independently, - ((CH 2) y} CH 2 O) -, or _{- ((CH 2) y CH} (CH 3) O) - a represents , Y each independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group, and acryloyl represented by X in the general formula (i). The total number of groups and methacryloyl groups is 3 or 4, and each m independently represents an integer of 0 to 10, and the total of m is 0 to 40. However, when the total of each m is 0, X In general formula (ii), the total of the acryloyl group and methacryloyl group represented by X is 5 or 6, and n is an integer of 0 to 10 each independently The total of n is 0 to 60. However, when the total of each n is 0, X Any one is a carboxyl group.) The colored radiation-sensitive composition according to any one of claims 1 to 6 , wherein the photopolymerization initiator is an oxime compound. A color filter using the colored radiation-sensitive composition according to any one of claims 1 to 7 . A step of forming a colored radiation-sensitive composition layer by applying the colored radiation-sensitive composition according to any one of claims 1 to 7 on a support, and the colored radiation-sensitive composition. A pattern forming method comprising: exposing a layer in a pattern; and developing the colored radiation-sensitive composition layer after exposure to form a colored pattern. The manufacturing method of a color filter including the process of forming a coloring pattern on a board | substrate using the pattern formation method of Claim 9 . A solid-state imaging device comprising the color filter according to claim 8 .