JP5743588B2 - Colored radiation-sensitive composition, pattern forming method, color filter manufacturing method, color filter, and solid-state imaging device - Google Patents

Description

  The present invention relates to a colored radiation-sensitive composition, a pattern formation method using the colored radiation-sensitive composition, a color filter manufacturing method, a color filter, and a solid-state imaging device.

The color filter is an indispensable component for solid-state imaging devices and liquid crystal displays.
A color filter for a solid-state image sensor is required to improve color separation and resolution.
In the improvement of color separation, a halogenated zinc phthalocyanine pigment has attracted attention as a pigment exhibiting suitable color separation as well as miniaturization of a pigment used as a colorant (see, for example, Patent Documents 1 and 2). The halogenated zinc phthalocyanine has a Tmax on the higher wavelength side even when the average particle diameter of the primary particles of the pigment is larger than that of the conventional halogenated copper phthalocyanine, which is a green pigment. Since it is very sharp, the color filter using it shows high color purity. Further, by adjusting the halogen atom content of the halogenated zinc phthalocyanine, the coloring power is improved and a high level of luminance is exhibited.

In addition, it is necessary to reduce stray light due to scattering as one of the means for improving the resolving power. For this reason, it is important to make the colored layer thin. The amount needs to be increased.
To increase the pigment loading, it is necessary to increase the pigment concentration in the colored radiation-sensitive composition. However, if the pigment concentration is increased, the dispersion resin and curable components (polymerization) in the colored radiation-sensitive composition will inevitably increase. The content of the functional compound, the photopolymerization initiator, etc.) is lowered, so that the storage stability and developability are deteriorated and the pattern forming property is deteriorated. In particular, the color filter for a solid-state imaging device has a very small pattern size due to an increase in the number of pixels and a reduction in size, resulting in a serious problem of deterioration in developability (residue suppression in unexposed areas).

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 image forming ability such as curability and the like with excellent adhesion to a substrate, ethylene dimer as a dispersing component is a copolymerization component It has been proposed to use a coloring composition using a binder and a graft copolymer and / or an acrylic block copolymer containing a nitrogen atom (see, for example, Patent Document 3).
However, in the manufacture 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 with a colored layer thickness of 1 μm or less is required. There has been a long-awaited improvement in the technology described above.

JP 2007-284589 A JP 2010-210702 A JP 2006-161035 A

A colored pixel having a coloring power with high color purity even in a thin layer needs to have the colorability of the pixel itself, but the color purity is lowered due to the following phenomenon.
The color filter is multicolored, and after the pixels are formed, colored pixels of other colors are 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 onto the previously formed pixel, and is different from the previously obtained pixel. A pattern with the colored radioactive composition of the next color is formed in place. However, the colored radiation-sensitive composition of the next color remains as a residue on the previously obtained pixel, or the colored radiation-sensitive composition of the next color penetrates into the previously formed pixel. This causes a phenomenon that the color purity of the pixel is lowered (hereinafter referred to as “residue mixed color”).

In addition, since the pixels in the color filter for the solid-state image sensor are adjacent to each other, the components of the colored radiation-sensitive composition diffuse from a pixel portion of another color arranged around the pixel by heating or the like. Then, the pixel receiving the diffused component and other colors in the peripheral portion are mixed, resulting in a phenomenon that the color purity of the pixel receiving the diffused component is lowered (hereinafter referred to as “diffused color mixing”).
Such residual color mixing and diffusion color mixing lower the color purity of the obtained color filter, and even if a colorant with high corner color purity and high coloring power is used, the effect is halved, and a solid-state imaging device with high resolving power 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.
An object of the present invention is to provide a colored radiation-sensitive composition capable of forming a colored cured film capable of suppressing residue color mixing and diffusion color mixing when a multicolor film is formed.
And it aims at providing the formation method of a pattern, the color filter which has high resolving power, its manufacturing method, and a solid-state image sensor using the said coloring radiation sensitive composition.

The present inventors have conducted intensive research in view of the above circumstances, and have found that (A) a halogenated zinc phthalocyanine pigment, (B) a binder having a specific structure, and (C) a polymerizable compound having a specific structure. The present invention has been completed by finding that the above-mentioned problems can be solved by an adhesive composition.
That is, the means for solving the above problems are as follows.

<1> (A) a zinc halide phthalocyanine pigment, (B) a copolymer component having 5.0 to 15.0 mol% and a radiation-sensitive group using a compound represented by the following general formula (1) as a copolymer component A binder containing 20 to 30 mol%, and (C) a polymerizable compound, wherein the polymerizable compound is selected from the group of compounds represented by the following general formula (Z-4) or (Z-5) A colored radiation-sensitive composition which is at least one kind .

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.
In the general formulas (Z-4) and (Z-5), E represents — (CH ₂ CH ₂ O) —, and X independently represents an acryloyl group or a methacryloyl group. A plurality of m's independently represent an integer of 0 to 10, and the total of each m is an integer of 2 to 16. A plurality of n's independently represent an integer of 0 to 10, and the total of each n is an integer of 3 to 24.

< 2 > The colored radiation-sensitive composition according to <1 >, wherein the (B) binder is a binder further having 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 (B) binder further includes (meth) acrylic acid as a copolymerization component.

< 4 > The colored radiation-sensitive composition according to any one of <1> to < 3 >, wherein the (B) binder includes the following repeating unit.

< 5 > The colored radiation-sensitive composition according to any one of <1> to < 4 >, wherein the (A) halogenated zinc phthalocyanine pigment is a compound represented by the following general formula (F).

In General Formula (F), X ^{1 to} X ¹⁶ each independently represent a chlorine atom, a bromine atom, or a hydrogen atom, and at least one of X ^{1 to} X ¹⁶ is a chlorine atom or a bromine atom.

< 6 > The colored radiation-sensitive composition according to any one of <1> to < 5 >, further comprising (D) a photopolymerization initiator.
< 7 > The colored radiation-sensitive composition according to < 6 >, wherein the (D) photopolymerization initiator is an oxime compound.

<8 > The colored radiation-sensitive composition according to any one of <1> to < 7 >, which is for a solid-state imaging device.
< 9 > The colored radiation-sensitive composition according to any one of <1> to < 8 > is applied onto a substrate to form a colored radiation-sensitive composition layer, and the colored radiation-sensitive composition. The pattern formation method which has the process of exposing a composition layer to pattern shape, and the process of developing the said colored radiation sensitive composition layer after exposure.
<1 0 > A color filter using the colored radiation-sensitive composition according to any one of <1> to < 8 >.

< 11 > The step of applying the colored radiation-sensitive composition according to any one of <1> to < 8 > on a substrate to form a colored radiation-sensitive composition layer, and the colored radiation-sensitive composition. A method for producing a color filter, comprising: exposing a composition layer in a pattern; and developing the colored radiation-sensitive composition layer after exposure.
< 12 > A solid-state imaging device comprising the color filter according to <1 0 >.

According to the present invention, it is possible to provide a colored radiation-sensitive composition capable of forming a colored cured film capable of suppressing residual color mixing and diffusion color mixing when forming a multicolor film.
Moreover, it is possible to provide a pattern forming method, a color filter having high resolving power, a method for manufacturing the same, and a solid-state imaging device using the colored radiation-sensitive composition.

Hereinafter, the colored radiation-sensitive composition, the pattern forming method, the color filter, the manufacturing method thereof, and the solid-state imaging device of the present invention will be described in detail.
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.

The colored radiation-sensitive composition of the present invention comprises (A) a zinc halide phthalocyanine pigment, (B) a compound represented by the general formula (1) described later as a copolymerization component of 5.0 to 15.0 mol%. A binder containing 20-30 mol% of a copolymer component having a radiation sensitive group, and (C) a polymerizable compound, wherein the polymerizable compound is represented by the following general formula (Z-4) or (Z-5) from the group of compounds represented by at least one member selected you characterized.
Hereinafter, each component which comprises the colored radiation sensitive composition of this invention is demonstrated in detail.

<(A) Halogenated zinc phthalocyanine pigment>
The colored radiation-sensitive composition of the present invention contains a halogenated zinc phthalocyanine pigment.
The zinc halide phthalocyanine pigment in the present invention is a pigment having a structure in which a total of 16 chlorine atoms and / or bromine atoms are bonded per phthalocyanine molecule (structure). As the number of chlorine and / or bromine atoms bonded to the phthalocyanine molecule increases, the hue of the zinc halide phthalocyanine pigment changes from blue to green.

  In order for the halogenated zinc phthalocyanine pigment to be green, it is preferable that the halogen atom bonded to the phthalocyanine molecule has 8 or more bromine atoms, and that 12 or more bromine atoms are more yellowish. It is more preferable in terms of coloring green with high brightness. In order to obtain a more yellowish green color, it is preferable that more bromine atoms are contained than chlorine atoms.

  Examples of the halogenated zinc phthalocyanine pigment include compounds represented by the following general formula (F).

In General Formula (F), X ^{1 to} X ¹⁶ each independently represent a chlorine atom, a bromine atom, or a hydrogen atom, and at least one of X ^{1 to} X ¹⁶ is a chlorine atom or a bromine atom.

The average primary particle diameter of the halogenated zinc phthalocyanine pigment is preferably 5 nm to 100 nm, more preferably 5 nm to 70 nm, still more preferably 5 nm to 50 nm, and most preferably 5 nm to 40 nm.
When the average primary particle diameter of the zinc halide phthalocyanine pigment is within the above range, for example, when it is contained in the colored radiation-sensitive composition used for forming the colored region of the rafilter in the present invention, the color purity is high. In addition, a color filter with high coloring power can be obtained.

  Here, the average primary particle diameter in the present invention refers to 100 primary particles of a zinc halide phthalocyanine pigment constituting an aggregate on a two-dimensional image obtained by photographing particles in a field of view with a transmission electron microscope. The average value of the longer diameter (major axis) and the shorter diameter (minor axis) is obtained and averaged.

  The halogenated zinc phthalocyanine pigment contained in the pigment dispersion of the present invention may be only one kind or a combination of plural kinds.

  Examples of combinations of zinc halide phthalocyanine pigments include, for example, zinc halides having a specific halogen atom composition, which are different from each other in the general formula (F), in which the number of halogen atoms selected from a bromine atom and a chlorine atom is different from each other. It may contain a phthalocyanine pigment in a specific ratio.

  The average composition of the halogenated zinc phthalocyanine pigment can be determined from mass spectrometry based on mass spectroscopy and halogen content analysis by flask combustion ion chromatography. Similarly, the content mol% of each halogenated zinc phthalocyanine pigment in the colored radiation-sensitive composition containing the halogenated zinc phthalocyanine pigment can be easily obtained by analyzing the result of mass spectrometry.

  The zinc halide phthalocyanine pigment can be produced, for example, by the method described in JP-A-2007-320986 and JP-A-2008-19383.

  There is no particular limitation on the method of pigmentation of zinc halide phthalocyanine. For example, zinc halide phthalocyanine before pigmentation may be dispersed in a dispersion medium and pigmented at the same time, but halogenated in a large amount of organic solvent. The solvent salt milling treatment is preferably employed in that pigment particles having a large specific surface area can be obtained more easily than the solvent treatment in which the metal phthalocyanine is heated and stirred.

This solvent salt milling process is a zinc halide phthalocyanine immediately after synthesis, or a zinc halide phthalocyanine (crude pigment) that has been ground and then not pigmented, an inorganic salt, and an organic solvent. It means the processing to crush.
When performing such a solvent salt milling treatment, it is preferable to use the latter crude pigment rather than the one immediately after synthesis. Specifically, a crude pigment, an inorganic salt, and an organic solvent that does not dissolve the inorganic salt used for milling are charged into a kneader, and kneading and grinding are performed therein. As a kneader at this time, for example, a kneader, a mix muller, or the like can be used.

<Other pigments>
The colored radiation-sensitive composition of the present invention may contain a known pigment other than the halogenated zinc phthalocyanine pigment.
In consideration of the fact that the color filter obtained by applying the colored radiation-sensitive composition of the present invention preferably has high color purity, other pigments are preferably as fine as possible. In consideration of the handling properties of the colored radiation-sensitive composition, the average primary particle size of other pigments is preferably 5 nm to 100 nm, more preferably 5 nm to 50 nm.

  As a known pigment other than the halogenated zinc phthalocyanine pigment used in the colored radiation-sensitive composition of the present invention, a conventionally known yellow pigment is preferable, and one or more 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.
Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36 : 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98 , 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176 177,179,180,181,182,185,187,188,193,194,199,213,214, etc.

Among the above yellow pigments, Pigment Yellow 139 or Pigment Yellow 185 is preferable, and Pigment Yellow 139 is more preferable in terms of color reproducibility.
The mass ratio of the zinc halide phthalocyanine and the yellow pigment is preferably 100: 5 to 100: 80, more preferably 100: 10 to 100: 65. In this range, the color purity is further increased and sufficient coloring power can be obtained.
The total content of pigments contained in the colored radiation-sensitive composition is preferably 20% by mass to 95% by mass, and 25% by mass to 90% by mass in the total solid content of the colored radiation-sensitive composition. Is more preferable, and 30% by mass to 80% by mass is still more preferable.
By setting the total content of the pigment within 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 film can be maintained, it is possible to prevent the development latitude during alkali development from becoming narrow.
In the present invention, the total solid content of the colored radiation-sensitive composition refers to the total mass of components excluding the organic solvent from the total composition of the colored radiation-sensitive composition.

The colored radiation-sensitive composition of the present invention is prepared in advance by dispersing the (A) halogenated zinc phthalocyanine pigment with a pigment dispersant, an organic solvent, a pigment derivative, and other components, if necessary, The obtained pigment dispersion (B) a binder containing a compound represented by the general formula (1) as a copolymerization component, (C) a polymerizable compound having one or more groups selected from a hydroxyl group and an oxyethylene group It is preferable to prepare a colored radiation-sensitive composition by mixing with other components added as necessary.
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 derivatives), 6750 (azo pigment derivatives) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co.,“ Polyflow No. 50E, No. .300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA-703-50, manufactured by Enomoto Kasei Co., Ltd. DA-705, DA-725 "," Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "manufactured by Kao Corporation," Homogenol L- 18 (polymer polycarboxylic acid) "," Emulgen 920, 930, 935, 85 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine) ”manufactured by Nippon Lubrizol Co., Ltd. , 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX, manufactured by Nikko Chemical Co., Ltd. ” (Polyoxyethylene monostearate), Kawaken Fine Chemical Co., Ltd. Hinoact T-8000E, Shin-Etsu Chemical Co., Ltd., Organosiloxane Polymer KP341, Yusho Co., Ltd. “W001: Cationic System Surfactant ", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester Nonionic surfactants such as, anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, manufactured by Morishita Sangyo Co., Ltd.” EFKA Polymer 401, EFKA Polymer 450 ”,“ Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid manufactured by San Nopco Corporation Polymeric dispersants such as “100”, 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.
Moreover, it is also a preferable aspect to use as a dispersant a binder containing 5.0 to 15.0 mol% of a compound represented by the following general formula (1) as a copolymerization component.

(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. As the organic solvent, esters, ethers, ketones, and aromatic hydrocarbons are used. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, diethylene glycol monoethyl ether acetate, diethylene glycol mono Butyl ether acetate, propylene glycol methyl ether, and propylene glycol monomethyl ether acetate are preferred.

  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 includes (B) general formula (1) from the viewpoint of improving dispersion stability and controlling developability when the pigment dispersion is applied to a colored radiation-sensitive composition. A binder containing 5.0 to 15.0 mol% of the compound represented by formula (1) as a copolymerization component and / or a polymer material having another structure may be further contained.

(B) A binder containing 5.0 to 15.0 mol% of the compound represented by the general formula (1) as a copolymerization component will be described later. Examples of other polymer materials having a structure include polyamidoamine and its binder. Salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer (especially polymerizable group in carboxylic acid group and side chain) (Meth) acrylic acid-based copolymers containing benzene, naphthalene sulfonic acid formalin condensate and the like. Such a polymer material is adsorbed on the surface of the pigment and acts to prevent re-aggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the pigment surface are used. Preferable examples include a graft copolymer including a monomer containing a heterocyclic ring and a polymerizable oligomer having an ethylenically unsaturated bond as a copolymer unit.
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, 20-80 mass% is preferable with respect to a pigment, 30-75 mass% is more preferable, 40-70 mass% is still more preferable.

<(B) Binder containing 5.0 to 15.0 mol% of the compound represented by the general formula (1) as a 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 of R ¹ and R ² in the general formula (1) may 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 contain 5.0 to 15.0 mol% of the compound represented by the general formula (1) as a copolymerization component, and further copolymerization other than the compound represented by the general formula (1). Ingredients may be included.
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 to contain (meth) acrylate and polyethyleneoxy (meth) acrylate 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, and examples of the alkyl (meth) acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, Acrylic acid esters having aliphatic hydroxyl groups such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, methacrylic acid esters, methyl acrylate, ethyl acrylate, acrylic Propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate Benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate, etc. Alkyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid 2-chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate And 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, propargyl methacrylate, and the like.

Moreover, it is preferable to contain (meth) acrylic acid containing an acidic group as a copolymerization component from a viewpoint of alkali developability.
Examples of (meth) acrylic acid include methacrylic acid and acrylic acid.

Examples of specific binders are shown below. The number attached to each structural unit is mol%.
“Me” represents a methyl group.

  Among these, it is advantageous from the viewpoint of solubility in a solvent and developability that the structure derived from the compound represented by the general formula (1) is a structure containing an oxane ring having a methoxycarbonyl group as a substituent. More preferred is a binder obtained by copolymerizing benzyl methacrylate, methyl methacrylate, and methacrylic acid as a copolymerization component.

In addition, a binder obtained by reacting a reactive component-containing monomer such as glycidyl methacrylate with (meth) acrylic acid, which is a copolymer component, can have a radiation-sensitive group in the specific binder of the present invention. It is.
As the specific binder of the present invention, the most preferable combination as a copolymerization component is a structure derived from methacrylic acid in a copolymer of the compound represented by the general formula (1), benzyl methacrylate, methyl methacrylate, and methacrylic acid. It is a specific binder having a radiation sensitivity by reacting a part with glycidyl methacrylate.

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 residue color mixture and diffusion color mixture can be enhanced.
The copolymer component for imparting oil solubility in the specific binder is preferably contained in the specific binder in an amount of 30 to 70 mol%, more preferably 40 to 60 mol%, and the solubility in a solvent is particularly improved.
It is preferable to contain 1-40 mol% of the copolymerization component containing the acidic group in a specific binder, and 5-30 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.
Among them, as a copolymerization component of the compound represented by the general formula (1), benzyl methacrylate is 40 to 50 mol%, glycidyl methacrylate is 20 to 30 mol%, methacrylic acid is 5 to 15 mol%, and methyl methacrylate. Is most preferred.

  Moreover, when making a specific binder contain a radiation sensitive group, 20-30 mol% in the specific binder is preferable as content of the copolymerization component which has a radiation sensitive group, In that case, it contains an acidic group. The polymerizable component and the polymerizable component for imparting oil solubility are each preferably 15 to 25 mol%. By setting it as this range, since the curability of the radiation-sensitive composition is increased, the effect of suppressing residual color mixing and diffusion color mixing can be further enhanced.

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

Part or all of the specific binder may be added in the preparation of the pigment dispersion described above.
One kind of specific binder may be included in the colored radiation-sensitive composition of the present invention, but two or more kinds may be included.
0.1-40 mass% is preferable with respect to the total solid of a colored radiation-sensitive composition, and, as for content of the specific binder in the colored radiation-sensitive composition of this invention, 1-30 mass% is more preferable. By making it within this range, the effect of the present invention is exhibited without regret.

<(C) Polymerizable compound>
The colored radiation-sensitive composition of the present invention comprises (C) a polymerizable compound, and the polymerizable compound is a polymerizable compound having one or more groups selected from a hydroxyl group and an oxyethylene group. To do. That is, in this invention, 1 or more types of polymeric compounds chosen from the polymeric compound which has a hydroxyl group, and the polymeric compound which has an oxyethylene group are contained.
As the polymerizable compound (C) in the present invention, one or more polymerizable compounds having at least one of a hydroxyl group and an oxyethylene group may be included, and the polymerizable compound includes both a hydroxyl group and an oxyethylene group. One or more of each may be included.
One or more of each of a polymerizable compound having a hydroxyl group and a polymerizable compound having an oxyethylene group may be contained.
Preferably, it contains at least one kind of each of a polymerizable compound having a hydroxyl group and a polymerizable compound having an oxyethylene group.
Hereinafter, the polymerizable compound having a hydroxyl group, the polymerizable compound having an oxyethylene group, and other polymerizable compounds that may be used will be described in detail.

(Polymerizable compound having a hydroxyl group)
The polymerizable compound having a hydroxyl group of the present invention is selected from compounds having a hydroxyl group and having at least one, preferably two or more polymerizable unsaturated bonds. Among these, a polyfunctional polymerizable compound having a hydroxyl group and having three or more polymerizable unsaturated bonds is preferable.
The polymerizable compound having a hydroxyl group of the present invention is preferable because it has three or more polymerizable unsaturated bonds, and is excellent in pattern forming property, and is prevented from residual color mixing and diffusion color mixing.

  Although the specific example of the polymeric compound which has a hydroxyl group in this invention is given below, it is not limited to this.

(Polymerizable compound having an oxyethylene group)
As the polymerizable compound having an oxyethylene group used in the colored radiation-sensitive composition of the present invention, the oxyethylene group as a linking group may be included in the molecule from 1 to 60, and preferably from 4 to 40, More preferably, 6 to 20 are included.
The polymerizable compound having an oxyethylene group preferably has at least one polymerizable unsaturated bond in the molecule, preferably two or more, and is a polyfunctional polymerizable compound containing three or more polymerizable unsaturated bonds. Is preferred.
The polymerizable compound having an oxyethylene group of the present invention is preferable because it contains three or more polymerizable unsaturated bonds, and is excellent in pattern forming property, and is prevented from residual color mixing and diffusion color mixing.

  The polymerizable compound having an oxyethylene group is preferably at least one selected from the group of compounds represented by the following general formula (Z-4) or (Z-5).

In the general formulas (Z-4) and (Z-5), each E independently represents — (CH ₂ CH ₂ O) —, and each X independently represents an acryloyl group or a methacryloyl group .
In the general formula (Z-4), the total number of acryloyl groups and methacryloyl groups is 3 or 4, and a plurality of m's each independently represents an integer of 0 to 10; Is an integer.
In the general formula (Z-5), the total number of acryloyl groups and methacryloyl groups is 5 or 6, and a plurality of n each independently represents an integer of 0 to 10, and the total of each n is 1 to 60. Is an integer.

In the general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 1-40 is preferable, the integer of 1-40 is more preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable.
In the general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 1-60 is preferable, the total of each n is more preferable, the integer of 3-24 is more preferable, and the integer of 6-12 is especially preferable.
In general formula (Z-4) or general formula (Z-5) in the _{- (CH 2 CH 2 O)} - may be in a form terminal oxygen atom side is bonded to X are preferred.

  The compound represented by the general formula (Z-4) or the general formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (Z-5), a form in which all six Xs are acryloyl groups is preferable.

  The compound represented by the general formula (Z-4) or the general formula (Z-5) is a conventionally known process, which is a ring opening of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by an addition reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a 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 (Z-4) or (Z-5).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
Specific examples include compounds represented by the following formulas (a) to (e) (hereinafter also referred to as “exemplary compounds (a) to (e)”), and among them, exemplary compounds (a) and ( b), (d) and (e) are preferred. The exemplified compound (c) is a polymerizable compound that also contains a hydroxyl group.
The oxyethylene group-containing polymerizable compound that can be used in the present invention is not limited to these examples.

  Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer. .

(Other polymerizable compounds)
In the present invention, other polymerizable compounds containing no hydroxyl group and oxyethylene group may be used in the colored radiation-sensitive composition of the present invention.
The other polymerizable compound that may be used in the present invention may have any structure as long as it is a compound containing a polymerizable unsaturated bond in the molecule.

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

As other polymerizable compounds, compounds having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure are also preferred. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso Propylene oxide added to polyfunctional alcohols such as anurate, glycerin and trimethylolethane and then (meth) acrylated, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, Japanese Patent Publication No. 51-37193 Urethane (meth) acrylates as described in each publication, polyester acrylates and epoxy resins described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of (meth) acrylic acid and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
In addition, preferable examples of other polymerizable compounds include a fluorene ring described in JP-A 2010-160418, JP-A 2010-129825, JP 4364216, etc., and an ethylenically unsaturated group. It is also possible to use a compound having two or more functions, a cardo resin.

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

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1), (MO-2), (MO-4), and (MO-5) are also suitable as other polymerizable compounds. Can be used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the said general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
In each of the polymerizable compounds represented by the general formulas (MO-1), (MO-2), (MO-4), and (MO-5), at least one of a plurality of Rs is —OC A group represented by (═O) CH═CH ₂ or —OC (═O) C (CH ₃ ) ═CH ₂ is represented.
Specific examples of the polymerizable compounds represented by the general formulas (MO-1), (MO-2), (MO-4), and (MO-5) include paragraph numbers in JP-A-2007-26979. The compounds described in 0248 to Paragraph No. 0251 can also be suitably used as other polymerizable compounds in the present invention.

  In addition, a compound obtained by adding propylene oxide or the like to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof is converted to other compounds. It can be used as a polymerizable compound.

  Among these, as other polymerizable compounds, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku) Dipentaerythritol penta (meth) acrylate (manufactured by Yakuhin Co., Ltd.) (KAYARAD D-310 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA as a commercial product; Nippon Kayaku) And a structure in which these (meth) acryloyl groups are interposed with propylene glycol residues or the like. These oligomer types can also be used. Preferred embodiments of other polymerizable compounds are shown below.

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

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

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

Moreover, it is also a preferable aspect to contain the polyfunctional monomer which has a caprolactone structure as another polymeric compound.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone modified polyfunctionality obtained by esterifying polyhydric alcohol such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone ( Mention may be made of (meth) acrylates. Especially, the polyfunctional monomer which has a caprolactone structure represented with the following general formula (Z-1) is preferable.

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

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

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

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

In addition, as another polymerizable compound in the present invention, in the compound represented by the general formula (Z-4) or (Z-5) mentioned in the section of the polymerizable compound containing an oxyethylene group, E is-(( A compound that is CH ₂ ) _y CH (CH ₃ ) O) — (where each y independently represents an integer of 0 to 10) can also be suitably used.

  Commercially available products of other polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include DPCA-, which is a hexafunctional acrylate having six pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd. 60, TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

As other polymerizable compounds, urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765 are also suitable. It is. Further, as other polymerizable compounds, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 By using a kind, a colored radiation-sensitive composition having an extremely excellent photosensitive speed can be obtained.
Commercially available products of other polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), Examples thereof include UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha).

About these polymerizable compounds, the details of the usage method such as the structure, single use or combination, addition amount and the like can be arbitrarily set according to the final performance design of the colored radiation-sensitive composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, from the viewpoint of increasing the strength of the colored radiation-sensitive composition film, those having three or more functional groups are preferable, and further, different functional groups / different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether type). A method of adjusting both sensitivity and strength by using a compound) is also effective. In addition, it is possible to control the developability of the colored radiation-sensitive composition by using tri- or more functional polymerizable compounds having different ethylene oxide chain lengths, and an excellent pattern forming ability can be obtained. preferable.
In addition, the selection of the polymerizable compound is also possible with respect to the compatibility and dispersibility with other components (for example, a photopolymerization initiator, a dispersion, an alkali-soluble resin, etc.) contained in the colored radiation-sensitive composition. The method of use is an important factor. For example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.

  In particular, in the present invention, the curability of the colored radiation-sensitive composition can be increased by including any one of a polymerizable compound containing a hydroxyl group and a polymerizable compound containing an oxyethylene group, The effect of suppressing the occurrence of residual color mixing and diffusion color mixing is exhibited while improving the pattern formability in development.

Furthermore, the effect of the present invention can be further enhanced by including, as the polymerizable compound, one or more selected from a polymerizable compound containing a hydroxyl group and one or more selected from a polymerizable compound containing an oxyethylene group. it can.
In particular, pentaerythritol triacrylate is effective as a polymerizable compound containing a hydroxyl group, and the exemplified compound (c) is effective as a polymerizable compound containing an oxyethylene group. By using both of these polymerizable compounds together, The effect can be greatly improved.

The content of any one of the polymerizable compound containing a hydroxyl group and the polymerizable compound containing an oxyethylene group in the colored radiation-sensitive composition of the present invention is the total amount in the colored radiation-sensitive composition. 0.1 mass%-70 mass% is preferable with respect to solid content, 1.0 mass%-50 mass% are more preferable, 2.0 mass%-40 mass% are especially preferable.
Moreover, the total content of the polymerizable compound including other polymerizable compounds in the colored radiation-sensitive composition of the present invention is 1.0% by mass to the total solid content in the colored radiation-sensitive composition. 80 mass% is preferable, 2.0 mass%-60 mass% is more preferable, 5.0 mass%-50 mass% is especially preferable.
Moreover, the total content of the polymerizable compound in the colored radiation-sensitive composition of the present invention is 5 with the dispersion resin in the radiation-sensitive composition and the compound represented by the following general formula (1) as a copolymerization component. 10 mass%-100 mass% are preferable with respect to the sum total of the binder which contains 0-15.0 mol%, 15 mass%-90 mass% are more preferable, and 20 mass%-80 mass% are especially preferable.
Furthermore, 0.1 mass%-5000 mass% are preferable with respect to the specific binder in a radiation sensitive composition, and, as for the total content of the polymeric compound in the radiation sensitive composition of this invention, 1.0 mass%. -4500 mass% is further more preferable, and 2.0 mass%-4000 mass% is especially preferable.

<(D) Photopolymerization initiator>
The radiation-sensitive composition of the present invention preferably 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 JP2010-15025A and US Patent Publication No. 2009-292209, in which a nitro group is introduced at the site, ketoxime compounds described in International Patent Publication No. 2009-131189, triazine skeleton and oxime skeleton are the same molecule A compound described in U.S. Pat. No. 7,556,910 and a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source may be used.

Preferably, it can also be suitably used for the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744. Among the cyclic oxime compounds, the cyclic oxime compounds fused to the carbazole dyes described in JP2010-32985A and JP2010-185072A in particular have high light absorptivity from the viewpoint of high sensitivity. preferable.
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 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 the 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 oberenyl group.

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

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

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

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

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

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

  In the 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 formula (OX-2) described later, and preferred examples are also the same.

In the 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 the 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 formula (OX-1), it is preferable from the viewpoint of sensitivity that the structure of “SAr” formed by Ar in the 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 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 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 Formula (OX-2), an alkyl group is preferable from the viewpoints of solvent solubility and improvement in absorption efficiency in the long wavelength region.
Moreover, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

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

  Among these, from the viewpoint of increasing sensitivity, the following structures are preferable.

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

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

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

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

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

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

  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 the production of a color filter of a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is important that the development be free of 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.

<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 Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like.
As an alkali-soluble resin containing these polymerizable groups, an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group; Urethane-modified polymerizable double bond-containing acrylic resin obtained by the above reaction, unsaturated group-containing acrylic obtained by reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule Resin, acid pendant type epoxy acrylate resin, OH group-containing acrylic resin and polymerizable double bond-containing acrylic resin obtained by reacting a polymerizable double bond, OH group-containing acrylic resin and isocyanate Resin obtained by reacting a compound having a polymerizable group, Japanese Patent Application Laid-Open No. 2002-229207 And a resin obtained by performing a basic treatment on a resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2003-335814 Etc. are preferable.

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

The acid value of the alkali-soluble resin 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 10 mass% or less with respect to content of the specific binder of this invention.

<Compound containing epoxy ring>
The colored radiation-sensitive composition of the present invention may contain a compound containing an epoxy ring.
By including a compound containing an epoxy ring, the strength of the colored pixel is improved.
The compound containing an epoxy ring is a compound having two or more epoxy rings in the molecule, such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound. For example, bisphenol A type includes Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. Toto Kasei), Denacol EX-1101, EX-1102, EX-1103, etc. (above Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (above Daicel Chemical), and similar The bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, 600 (manufactured by Daicel UCB) can also be used. As cresol novolac type, Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704 etc. (above manufactured by Tohto Kasei), Denacol EM-125 etc. Examples of cycloaliphatic epoxy compounds such as 3,5,3 ', 5'-tetramethyl-4,4'diglycidylbiphenyl include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT- 401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100 (manufactured by Toto Kasei) and the like. Also 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid diester In addition, glycidyl ester, Epototo YH-434 and YH-434L which are amine type epoxy resins, glycidyl ester in which dimer acid is modified in the skeleton of bisphenol A type epoxy resin, and the like can also be used.

Among these, “molecular weight / number of epoxy rings” is preferably 100 or more, and more preferably 135 to 350. If the “molecular weight / number of epoxy rings” is small, the curability is high, the shrinkage at the time of curing is large, and if it is too large, the curability is insufficient and the reliability is poor or the flatness is poor.
Specific preferred compounds include Epototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, Plaxel GL-61, GL-62, 3,5,3 ′, 5′-tetramethyl. -4,4 'diglycidyl biphenyl, ceroxide 2021, 2081, Epolide GT-302, GT-403, EHPE-3150, etc., which have a "molecular weight / number of epoxy rings" of 135-350.

<Thermal polymerization initiator>
The colored radiation-sensitive composition of the present invention may contain a thermal polymerization initiator.
As the thermal polymerization initiator, generally known organic peroxide compounds can be used.
In the present invention, it is preferable to contain an organic peroxide or an azo compound as the thermal polymerization initiator. As a result, the effect of the present invention becomes more remarkable. In addition to the thermal polymerization initiator, a curing catalyst such as imidazole can also be used. The organic peroxide compound and the azo compound can be used in combination of two or more in addition to the single use. Here, the organic peroxide is a derivative of hydrogen peroxide (H—O—O—H) and refers to an organic compound having a —O—O— bond in the molecule.

When classified by chemical structure, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates and the like can be mentioned.
Specifically, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, benzoyl peroxide, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, t-butyl peroxybenzoate, di-t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, t-butyl Peroxyacetate, t-hexyl peroxybenzoate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2 Ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis (m -Toluylperoxy) hexane, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisobutyrate, 1,1,3,3- Tetramethylbutyl peroxy-2-ethylhexanoate, t-hexyl peroxyisopropyl monocarbonate, 2,5-dimethyl-2,5-bis (2-ethylhexinoyl peroxy) hexane, t-butyl peroxy-2-ethylhexanoate , T-butyl peroxy maleic acid, cyclohexanone peroxide, methyl acetoacetate peroxide, methyl hexanone peroxide, acetylacetone peroxide, 1,1-bis (t-hexyl proxy) -3,3,5-to Methylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) ) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (4,4-di-t-butyl) Peroxycyclohexyl) propane, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, etc. are preferred, and 2,2-bis (4 4-di-t-butylperoxycyclohexyl) propane and other peroxyketals Things; diacyl peroxides compounds such as benzoyl peroxide; peroxy ester compounds such as t- butyl peroxybenzoate are preferred. Examples of the azo compound include 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide (2- (carbamoylazo) isobutyro Nitrile) and the like.

Among these compounds, a compound that has a decomposition temperature that is somewhat high and is stable at room temperature, is a compound that decomposes when heated to generate radicals and serves as a polymerization initiator.
The content of the organic peroxide-based or azo-based compound (thermal polymerization initiator) is preferably 0.5 to 20% by mass, more preferably based on the amount of the compound containing an epoxy ring that is a thermopolymerizable compound. Is 1 to 15% by mass. When the blending amount of the organic peroxide compound and the azo compound is less than 0.5% by mass, the effect may be reduced, and when it exceeds 20% by mass, the viscosity of the composition may change over time. . Further, among organic peroxide compounds and azo compounds, when a compound having a relatively high half-life temperature (preferably 50 ° C. or higher, more preferably 80 ° C. or higher) is used, the viscosity of the composition changes with time. It can be suitably configured without doing. These initiators can be used alone or in combination of two or more.

<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.
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, phthalocyanine, benzopyran, and indigo 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.

<Ultraviolet absorber>
The colored radiation-sensitive composition of the present invention may contain an ultraviolet absorber.
As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and the like. Examples of benzophenone-based UV absorbers include 2,2′-dihydroxy-4- Methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- And hydroxy-4-octoxybenzophenone. Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3). '-Tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- ( 2'-hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzoto Azole, 2- [2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole and the like.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, and the like. Furthermore, as an example of a triazine ultraviolet absorber, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) ) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as 1,3,5-triazine and 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy); 3-methyl-4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6 Bis (hydroxyphenyl) triazine compounds such as-(2,4-dimethylphenyl) -1,3,5-triazine; 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4- Dibutoxyphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris [2- And tris (hydroxyphenyl) triazine compounds such as hydroxy-4- (3-butoxy-2-hydroxypropyloxy) phenyl] -1,3,5-triazine.
Moreover, the brand name UV-503 (Daito Chemical Co., Ltd. product) which is a commercial item can also be used.

In the present invention, the various ultraviolet absorbers may be used alone or in combination of two or more.
The colored radiation-sensitive composition may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is based on the total solid mass of the colored radiation-sensitive composition of the present invention. The content is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.

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

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

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

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

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

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

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

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

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

  Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.

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

<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 residual undissolved coloring composition while maintaining high pattern adhesion. .

<Other ingredients>
In the colored radiation-sensitive composition of the present invention, a chain transfer agent such as N, N-dialkylaminobenzoic acid alkyl ester and 2-mercaptobenzothiazole, an azo compound, a peroxide compound, etc. Thermal polymerization initiator, thermal polymerization component, UV absorber such as polyfunctional thiol, epoxy compound, alkoxybenzophenone, nonionic surfactant (for example, PIONIN D6112W, D6315 from Takemoto Yushi) ) Development accelerators, plasticizers such as dioctyl phthalate, developability improvers such as low molecular weight organic carboxylic acids, other fillers, polymer compounds other than the above specific binders and alkali-soluble resins, antioxidants, and aggregation inhibitors Various additives such as can be contained.
Further, a thermosetting agent can be added to increase the degree of curing of the film by post-heating after development. Examples of the thermosetting agent include thermal polymerization initiators such as azo compounds and peroxides, novolac resins, resole resins, epoxy compounds, and styrene compounds.

-Preparation of colored radiation-sensitive composition-
The colored radiation-sensitive composition of the present invention is preferably prepared using an organic solvent together with the above-described components.
Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, isoamyl acetate, isobutyl acetate, amyl formate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, Methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3-methoxypropionate Acid methyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-methoxypropionate Methyl acetate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2-methyl Ethyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid Methyl, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons such as toluene, xylene and the like can be mentioned.

Among these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, Butyl carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using independently.

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

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

  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 onto a substrate (colored layer forming step), and the radiation-sensitive property. It has the process (exposure process) which exposes a composition layer in pattern shape, and the process (development process) which develops the said radiation sensitive composition layer after exposure.

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 pattern forming method and the color filter of the present invention will be described in detail through the color filter and the manufacturing method thereof (the manufacturing method of the color filter of the present invention).

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

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

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

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

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

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

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

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

The developer is preferably an organic alkali developer that does not cause damage to the underlying circuit. 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.

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

  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.

[Solid-state imaging device]
The solid-state imaging device of the present invention includes the color filter described above. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter of the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. .

A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on the support, and the transfer electrodes are formed on the photodiodes and the transfer electrodes. Having a light-shielding film made of tungsten or the like that is opened only in the light-receiving part of the photodiode, and having a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part, It is the structure which has the color filter for solid-state image sensors of this invention on a device protective film.
Further, a configuration having light collecting means (for example, a microlens, etc., the same shall apply hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light collecting means on the color filter. Etc.
The color filter of the present invention is particularly suitable for a high-resolution CCD or CMOS solid-state imaging device having more than 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.

  Further, the color filter of the present invention manufactured by the method for manufacturing 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 can be used for electronic paper, a liquid crystal display device, and an organic EL display device. It can be suitably used for image display devices such as the above.

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.
The following “Examples 1, 2, 3, 4, 7 , 11 , 13, 14, 15 and 16 ” are “Reference Examples 1, 2, 3, 4, 7 , 11 , 13, 14, 15 and 16 ".

(Binder synthesis)
(Synthesis of binder 1)
A solution having the following composition was prepared in a monomer dropping container.
15 parts of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (hereinafter referred to as “DM”) 60 parts of benzyl methacrylate (hereinafter referred to as “BzMA”) methyl methacrylate (Hereinafter referred to as “MMA”) 17 parts • Methacrylic acid (hereinafter referred to as “MAA”) 40 parts • 2 parts of t-butylperoxy-2-ethylhexanoate • 25 parts of diethylene glycol dimethyl ether

A solution having the following composition was prepared in a container for dropping a chain transfer agent.
・ 4 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 container and the chain transfer agent dropping container, 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”) 40 parts ・ 2,2′-methylenebis (4-methyl-6-tert-butylphenol) 0.2 part ・ Triethylamine 0.4 part Cooling to room temperature after completion of the reaction 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 20 parts BzMA 65 parts MMA 9 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.
GMA 60 parts 2,2'-methylenebis (4-methyl-6-t-butylphenol) 0.2 parts Triethylamine 0.4 parts 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 20 parts BzMA 80 parts MMA 9 parts MAA 25 parts t-butylperoxy-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.
・ 43 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 20 parts ・ BzMA 65 parts ・ MMA 13 parts ・ MAA 8 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.
・ 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.
GMA 15 parts 2,2′-methylenebis (4-methyl-6-tert-butylphenol) 0.2 part Triethylamine 0.4 part 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.
・ DM 5 parts ・ BzMA 45 parts ・ MMA 8 parts ・ MAA 18 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.
・ 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.
• GMA 30 parts • 2,2′-methylenebis (4-methyl-6-tert-butylphenol) 0.2 part • Triethylamine 0.4 part 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 5 (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 5. 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 20 parts ・ BzMA 55 parts ・ MMA 7 parts ・ MAA 10 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.
・ 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.
GMA 15 parts 2,2′-methylenebis (4-methyl-6-tert-butylphenol) 0.2 part Triethylamine 0.4 part 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 6 (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 6. The weight molecular weight was measured by GPC.

  Table 1 summarizes the composition (mol%) of the constituent 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 a composition ratio (mol%) of a structure in which GMA is added to a structural unit derived from MAA.

(Preparation of pigment dispersion)
(Preparation of Green pigment dispersion G1)
15.1 parts of Pigment Green 58 which is a partially brominated zinc phthalocyanine pigment as a pigment, 7.2 parts of BYK-161 (manufactured by BYK) as a pigment dispersant, and propylene glycol methyl ether acetate (hereinafter “PGMEA” as an organic solvent) The mixed liquid consisting of 77.7 parts was mixed and dispersed by a bead mill for 15 hours to prepare Green pigment dispersion G1.

(Preparation of Yellow pigment dispersion Y1)
A mixed solution of 12.9 parts of Pigment Yellow 139 as a pigment, 5.2 parts of BYK-161 (manufactured by BYK) as a pigment dispersant, and 81.9 parts of PGMEA as an organic solvent is mixed and dispersed for 15 hours by a bead mill. Then, a Yellow pigment dispersion Y1 was prepared.

(Preparation of Blue pigment dispersion B1)
Pigment Blue 15: 6 9.5 parts as pigment, Pigment Violet 23 2.4 parts, BYK-161 (manufactured by BYK) 5.6 parts as a pigment dispersant, and 82.5 parts of PGMEA, Blue pigment dispersion B1 was prepared by mixing and dispersing with a bead mill for 15 hours.

(Preparation of Red pigment dispersion R1)
A mixed solution consisting of 8.3 parts of Pigment Red 254 as pigment and 3.7 parts of Pigment Yellow 139, 4.4 parts of BYK-161 (manufactured by BYK) as pigment dispersant, and 83.6 parts of PGMEA By mixing and dispersing for 15 hours, a Red pigment dispersion R1 was prepared.

Example 1
[Preparation of colored radiation-sensitive composition]
(Preparation of Green-colored radiation-sensitive composition (coating solution) A-1)
The pigment dispersion liquids G1 and Y1 were mixed and stirred so as to have the following composition, and then filtered through a 0.6 μm pore size polypropylene filter to prepare a colored radiation-sensitive composition A-1.
<Composition>
-Pigment dispersion: Green pigment dispersion G1 54.2 parts-Pigment dispersion: Yellow pigment dispersion Y1 30.7 parts-Photopolymerization initiator: IRGACURE OXE-01 (the following structure manufactured by BASF Corporation) 0.87 Part / polymerizable compound: polymerizable compound (A) (structure shown below) 2.1 part / polymerizable compound: polymerizable compound (B) (structure shown below) 2.1 part / binder: binder 1 in the above synthesis example 3 parts ・ Polymerization inhibitor: p-methoxyphenol 0.002 part ・ Epoxy curable resin: EHPE-3105 (manufactured by Daicel Chemical Industries, Ltd.) 1.15 parts ・ Ultraviolet absorber: UV-503 (Daito Chemical Co., Ltd.) 0.69 part ・ Organic solvent: PGMEA 7.1 part ・ Surfactant: PGMEA 0.2% solution of F-781 (manufactured by DIC Corporation) 0.83 part

<< Examples 2 to 16 and Comparative Examples 1 to 10 >>
As Examples 2 to 16 and Comparative Examples 1 to 10, in the preparation of the colored radiation-sensitive composition A-1 of Example 1, the types of binders and the types and mixing ratios of polymerizable compounds are shown in Table 2. Otherwise, the colored radiation-sensitive compositions A-2 to A-16 of Examples 2 to 16 and Comparative Examples 1 to 10 are the same as in the preparation of the colored radiation-sensitive composition A-1. And A-18 to A-27 were prepared.

<< Example 17 >>
In Example 5, as a polymerizable compound, a polymerizable compound (C) which is a silane coupling agent having a polymerizable group was added to prepare a colored radiation-sensitive composition A-17 of Example 17. At that time, the total amount of the polymerizable compound was not changed, and the ratio was shown in Table 2.

(Preparation of Blue colored radiation-sensitive composition (coating solution))
・ Pigment dispersion: 51.2 parts of Blue pigment dispersion B1 ・ Photopolymerization initiator: IRGACURE OXE-01 (manufactured by BASF) 0.87 parts ・ Polymerizable compound: 3.5 parts of polymerizable compound (B) Polymerizable compound: KAYARAD RP-1040 (the following structure, manufactured by Nippon Kayaku Co., Ltd.) 1.2 parts Binder: 6.3 parts of binder (I) having the following structure Binder: ACA230AA (the following structure, Daicel Chemical Industries) 1.1 part ・ Polymerization inhibitor: 0.002 part ・ Additive: Pionein D-6112-W (manufactured by Takemoto Yushi Co., Ltd.) 0.19 part ・ Silane coupling agent: 10.8 parts of cyclohexanone 0.9% solution of KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd.), organic solvent: 14.3 parts of PGMEA, organic solvent: 6.4 parts of cyclohexanone, fluorosurfactant: F-781 Cyclohexanone 0.2% solution of DIC Corporation 4 2 parts

(Preparation of Red colored radiation-sensitive composition (coating solution))
Pigment dispersion: 62.1 parts of Red pigment dispersion R1 Photopolymerization initiator: IRGACURE OXE-02 (manufactured by BASF Co., Ltd.) 0.68 parts Polymerizable compound: Polymerizable compound (A) 6 parts Polymerizable compound: KAYARAD RP-1040 (Nippon Kayaku Co., Ltd.) 1.6 parts Binder: 1.7 parts of the following structure (I) Polymerization inhibitor: p-methoxyphenol 0.002 part Additive: 0.72 part Pionein D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Silane coupling agent: 5.5 parts cyclohexanone solution of KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd.) 5.5 parts, organic solvent : PGMEA 11.2 parts-Organic solvent: Ethyl 3-ethoxypropionate (hereinafter referred to as "EEP") 10.9 parts-Fluorosurfactant: EEP of F-781 (manufactured by DIC Corporation). 4.2 parts of 2% solution

  The components used in the above, Examples and Comparative Examples are summarized below.

[Evaluation]
The following evaluation was performed using Green colored radiation-sensitive compositions A-1 to A-31 shown in the composition of Table 2. The evaluation results are collectively shown in Table 2.
<Preparation of glass wafer with undercoat layer for evaluation>
A coating film is formed by uniformly applying AP-3000 (manufactured by The Dow Corning Chemical Co., Ltd.), a curable transparent composition, on an 8-inch glass wafer by spin coating, and the formed coating film is 220 ° C. In the oven for 60 minutes. The spin coating speed was adjusted so that the thickness of the coating film after the heat treatment was about 1 μm.
A glass wafer with an undercoat layer was obtained as described above.

<Evaluation of residual color mixture>
The green colored radiation-sensitive composition A-1 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 180 seconds using a 100 ° C. hot plate. Heat treatment (pre-baking) was performed.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Co., Ltd.), 365 nm wavelength light was solid-exposed at 1000 mJ / cm ² .
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 layer on the glass wafer.
A glass wafer on which a green colored layer is formed is fixed to the horizontal rotary table by a vacuum chuck method, and pure glass is spouted from above the rotation center while rotating the glass wafer at a rotation speed of 50 rpm by a rotating device. It was supplied in the form of a shower, rinsed, and then spray dried.
Further, heat treatment (post-baking) was performed for 300 seconds using a 200 ° C. hot plate to obtain a cured green colored layer.

The blue colored radiation-sensitive composition is applied onto the cured green colored layer using a spin coater so that the film thickness after drying is 1.0 μm, and heated for 180 seconds using a hot plate at 100 ° C. The treatment (pre-baking) was carried out to obtain a laminated colored layer in which a second blue colored radiation-sensitive composition layer was formed on the cured green colored layer.
Subsequently, the blue colored layer was developed and removed by performing development, rinsing, and drying in the same manner as when the obtained colored layer of the laminate was applied to the first green colored layer.

Spectral variation (ΔT% max) of maximum transmittance after the first layer of hardened green colored layer and after the development removal of the second layer was measured using MCPD-3000 (Otsuka Electronics Co., Ltd.). Measurement was made to evaluate the residual color mixture of the second blue colored radiation-sensitive composition remaining on the first cured green colored layer. The smaller the variation, the more difficult the color mixing of the residue, which is more desirable. Although it determined with the following criteria, the criteria 3 or more are practical.
~ Criteria ~
5: ΔT% max <0.5%
4: 0.5% ≦ ΔT% max <1.0%
3: 1.0% ≦ ΔT% max <3.0%
1: 3.0% ≦ ΔT% max

<Diffusion color mixture evaluation>
The green colored radiation-sensitive composition A-1 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 180 seconds using a 100 ° C. hot plate. Heat treatment (pre-baking) was performed.
Next, using an i-line stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.), the exposure amount is adjusted so that the pattern size becomes 3.0 μm square through a 3.0 μm square Bayer pattern mask at a wavelength of 365 nm. And exposed.
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, a heat treatment (post-bake) was performed for 300 seconds using a 200 ° C. hot plate to obtain a single color filter having green pixels on which a colored Bayer pattern was formed.
Next, the blue colored radiation-sensitive composition B1 is applied using a spin coater on the single color filter having the green pixel created as described above so that the film thickness after drying becomes 0.8 μm. Heat treatment (pre-baking) was performed for 180 seconds using a hot plate.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at 400 mJ / cm ² so as to be adjacent to a green pixel through a 3.0 μm square island pattern mask at a wavelength of 365 nm. .
The glass wafer on which the colored layer thus obtained is laminated is developed, rinsed, dried, and post-baked in the same manner as the green pixel formation, and has 2 green Bayer pattern pixels and 2 blue island pattern pixels. A color filter of color was obtained.

Next, Red colored radiation-sensitive composition R1 is applied onto a glass wafer having two color filters using a spin coater so that the film thickness after drying is 0.65 μm, and a hot plate at 100 ° C. is used. Then, heat treatment (pre-baking) was performed for 180 seconds.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), it is 150 mJ so as to be adjacent to the green pixel through the 3.0 μm square island pattern mask at a wavelength of 365 nm and not to overlap the blue pixel. / Cm < ² >.
The glass wafer on which the colored layers thus obtained are laminated is developed, rinsed, dried, and post-baked in the same manner as the green pixel formation, and the green Bayer pattern, the blue island pattern, and the red island pattern are formed. A three-color color filter having

Spectroscopy of the red pixel portion of the three color filters obtained above was measured using a microspectrophotometer LVmicro-V (manufactured by Lambda Vision Co., Ltd.), and this was used as initial spectroscopy.
Next, the above three color filters are heat-treated for 60 minutes using a 200 ° C. hot plate, and the spectrophotometer LVmicro-V (manufactured by Lambda Vision Co., Ltd.) is used to measure the spectrum. Spectroscopic.
Diffusion color mixing was evaluated based on the difference in light absorption intensity at 650 nm between the initial spectrum and the processed spectrum. A smaller difference is more desirable because it is less likely to cause diffuse color mixing. Although it determined with the following criteria, the criteria 3 or more are practical.
~ Criteria ~
5: Δ absorbance intensity (650 nm) <0.02
4: 0.02 ≦ Δ absorbance intensity (650 nm) <0.04
3: 0.04 ≦ Δ Absorption intensity (650 nm) <0.08
1: 0.08 ≦ Δ absorption intensity (650 nm)

  In Table 2, KAYARAD DPHA is dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.). Moreover, the level which described 2 types as a polymeric compound is mixing ratio 50:50 (mass ratio), and the level which used 3 types is colored radiation-sensitive radiation which is a mass ratio of 40:40:20 in order of description. It constitutes a polymerizable compound of the adhesive composition.

  From Table 2, according to the colored radiation-sensitive composition of the present invention, the color component of the green pixel is not affected by the residue due to the color filter to be laminated next, and the adjacent pixel after heating after pattern formation. It can be seen that does not move. From this, according to the colored radiation-sensitive composition of the present invention, it is possible to provide a color filter without changing the spectrum of the green pixel portion and the adjacent pixel portion.

Claims (12)

(A) Zinc halide phthalocyanine pigment, (B) Copolymerization component 20 to 30 having 5.0 to 15.0 mol% and a radiation sensitive group using a compound represented by the following general formula (1) as a copolymerization component A binder containing mol%, and (C) a polymerizable compound, wherein the polymerizable compound is selected from the group of compounds represented by the following general formula (Z-4) or (Z-5) A colored radiation-sensitive composition.


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.
In the general formulas (Z-4) and (Z-5), E represents — (CH ₂ CH ₂ O) —, and X independently represents an acryloyl group or a methacryloyl group. A plurality of m's independently represent an integer of 0 to 10, and the total of each m is an integer of 2 to 16. A plurality of n's independently represent an integer of 0 to 10, and the total of each n is an integer of 3 to 24. The colored radiation-sensitive composition according to claim 1, wherein the (B) binder is a binder further having an aryl (meth) acrylate or an alkyl (meth) acrylate as a copolymerization component. (B) the binder further (meth) colored radiation-sensitive composition according to claim 1 or claim 2 as a binder having an acrylic acid as a copolymerization component. The colored radiation-sensitive composition according to any one of claims 1 to 3 , wherein the (B) binder contains the following repeating unit.

The colored radiation-sensitive composition according to any one of claims 1 to 4 , wherein the (A) halogenated zinc phthalocyanine pigment is a compound represented by the following general formula (F).


In General Formula (F), X ^{1 to} X ¹⁶ each independently represent a chlorine atom, a bromine atom, or a hydrogen atom, and at least one of X ^{1 to} X ¹⁶ is a chlorine atom or a bromine atom. The colored radiation-sensitive composition according to any one of claims 1 to 5 , further comprising (D) a photopolymerization initiator. The colored radiation-sensitive composition according to claim 6 , wherein the photopolymerization initiator (D) is an oxime compound. The colored radiation-sensitive composition according to any one of claims 1 to 7 , which is used for a solid-state imaging device. The process of providing the colored radiation-sensitive composition of any one of Claims 1-8 on a board | substrate, and forming a colored radiation-sensitive composition layer, The said colored radiation-sensitive composition layer The pattern formation method which has the process of exposing to a pattern form, and the process of developing the said colored radiation sensitive composition layer after exposure. A color filter using the colored radiation-sensitive composition according to any one of claims 1 to 8 . The process of providing the colored radiation-sensitive composition of any one of Claims 1-8 on a board | substrate, and forming a colored radiation-sensitive composition layer, The said colored radiation-sensitive composition layer A method for producing a color filter, comprising: exposing the film in a pattern; and developing the colored radiation-sensitive composition layer after exposure. A solid-state imaging device having a color filter according to claim 1 0.