JP2009258657A - Photosensitive resin composition, light-shielding color filter, method of producing the same, and solid-state image sensor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of forming a light-shielding color filter suppressed in the reduction of light shielding performance at the periphery thereof. <P>SOLUTION: The photosensitive resin composition includes a black colorant, a photo-polymerized compound, resin, a photo-polymerization initiator and a solvent. The composition can form the light-shielding color filter having a ratio [OD<SB>1200</SB>/OD<SB>365</SB>] of optical density (OD<SB>1200</SB>) at a wavelength of 1,200 nm to optical density (OD<SB>365</SB>) at a wavelength of 365 nm of 0.5 to 3. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition, a light-shielding color filter, a method for producing the same, and a solid-state imaging device.

A color filter used in a liquid crystal display device is provided with a light-shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast. A solid-state image sensor is also provided with a light-shielding color filter for the purpose of preventing noise and improving image quality.
A photosensitive resin composition containing a black color material such as carbon black or titanium black is known as a composition for forming a black matrix for a liquid crystal display device or a light-shielding color filter for a solid-state imaging device. (For example, refer to Patent Documents 1 to 5).

Japanese Patent Laid-Open No. 10-246955 JP-A-9-54431 Japanese Patent Laid-Open No. 10-46042 JP 2006-36750 A JP 2007-115921 A

The black matrix for liquid crystal display devices is mainly required to block light in the visible range, while the light-blocking color filter for solid-state imaging devices has light blocking in the infrared region in addition to the light blocking property in the visible region. It is necessary to prepare.
While the black matrix for liquid crystal display devices is required to be miniaturized, the light-shielding color filter for solid-state image sensors (especially, the surface opposite to the light-receiving element forming surface of the support (hereinafter referred to as “back surface”). The light-shielding color filter for shielding light) is required to uniformly shield light over a larger area than the black matrix for liquid crystal display devices.

  However, when a light-shielding color filter having a large area is formed using the above-described conventional photosensitive resin composition as a light-shielding color filter for a solid-state imaging device, the thickness of the light-shielding color filter is smaller in the periphery than in the central portion. (Step region) may occur, and the light shielding ability of the peripheral portion may be lowered.

This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, the present invention provides a photosensitive resin composition capable of forming a light-shielding color filter in which a decrease in light-shielding ability in the peripheral portion is suppressed, a light-shielding color filter in which a decrease in light-shielding ability in the peripheral portion is suppressed, and An object of the present invention is to provide a manufacturing method thereof, and to provide a solid-state imaging device with less noise and excellent color reproducibility.

Specific means for solving the above-described problems are as follows.
<1> An optical density at a wavelength of 1200 nm (OD ₁₂₀₀ ) and an optical density at a wavelength of 365 nm (OD) when at least a black color material, a photopolymerizable compound, a resin, a photopolymerization initiator, and a solvent are used to form a light-shielding color filter. ₃₆₅ ) is a photosensitive resin composition having a ratio [OD ₁₂₀₀ / OD ₃₆₅ ] of 0.5 or more and 3 or less.

<2> The photosensitive resin composition according to <1>, wherein the light-shielding color filter has an optical density in a wavelength region of 900 nm to 1300 nm of 2 or more and 10 or less.
<3> The photosensitive resin composition according to <1> or <2>, wherein the black color material contains titanium black.
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the photopolymerization initiator includes an oxime photopolymerization initiator.
<5> The photosensitive resin composition according to any one of <1> to <4>, which is used for forming a light-shielding color filter for a solid-state imaging device.
<6> The photosensitivity as described in any one of <1> to <5>, wherein the content of the photopolymerization initiator in the total solid content is 3% by mass or more and 20% by mass or less. It is a resin composition.

<7> An optical density at a wavelength of 1200 nm (OD ₁₂₀₀ ) and an optical density at a wavelength of 365 nm (OD ₃₆₅ ), formed using the photosensitive resin composition according to any one of <1> to <6>. The light-shielding color filter has a ratio [OD ₁₂₀₀ / OD ₃₆₅ ] of 0.5 or more and 3 or less.
<8> The light-shielding color filter according to <7>, wherein an optical density in a wavelength region of 900 nm to 1300 nm is 2 or more and 10 or less.

<9> After having coated the photosensitive resin composition according to any one of <1> to <6> on a support, exposing through a mask, developing, and forming a pattern, This is a method for producing a light-shielding color filter.
<10> A solid-state imaging device comprising the light-shielding color filter according to <7> or <8>.

  According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a light-shielding color filter in which a decrease in light-shielding ability in the peripheral portion is suppressed, a light-shielding color filter in which a decrease in light-shielding ability in the peripheral portion is suppressed, and It is possible to provide a manufacturing method thereof and a solid-state imaging device with less noise and excellent color reproducibility.

It is a schematic diagram which shows a mode that the step arose in the light-shielding color filter.

≪Photosensitive resin composition≫
The photosensitive resin composition of the present invention includes at least a black color material, a photopolymerizable compound, a resin, a photopolymerization initiator, and a solvent. When a light-shielding color filter is obtained, an optical density (OD ₁₂₀₀ ) at a wavelength of 1200 nm is obtained. The ratio [OD ₁₂₀₀ / OD ₃₆₅ ] with the optical density (OD ₃₆₅ ) at a wavelength of 365 nm is configured to be 0.5 or more and 3 or less.
By forming the photosensitive resin composition in the above-described configuration, when a light-shielding color filter is formed using the photosensitive resin composition, a region where the film thickness is thinner than the central portion in the periphery of the light-shielding color filter (step Region) can be suppressed, and a decrease in light shielding ability in the peripheral portion can be suppressed.
When the [OD ₁₂₀₀ / OD ₃₆₅ ] is less than 0.5, the light shielding property in the infrared region required as a light shielding color filter for a solid-state imaging device is insufficient. On the other hand, when [OD ₁₂₀₀ / OD ₃₆₅ ] exceeds 3, the balance between the light shielding ability in the visible region and the infrared region is lost, which is not preferable.

  In the present invention, the “light-shielding color filter” means a light-shielding pattern obtained by exposing and developing a photosensitive resin composition containing at least a black color material, a photopolymerizable compound, a resin, a photopolymerization initiator, and a solvent. Say. The color of the “light-shielding color filter” in the present invention may be an achromatic color such as black or gray, or a gray color mixed with a chromatic color.

In the present invention, the step means a step observed in a light-shielding color filter having a side of about 50 μm or more (particularly, about 200 μm or more) formed by applying, exposing and developing a photosensitive resin composition. When the light-shielding color filter is observed from above the film surface with an optical microscope, the step may be observed as a line that is substantially similar to the pattern edge of the light-shielding color filter.
FIG. 1 is a diagram schematically showing a state in which steps are generated in the light-shielding color filter 10. The solid line represents the pattern edge 1 of the light-shielding color filter, and the broken line represents step 2. Actually, the broken line is observed as a solid line. The film thickness of the light-shielding color filter is the area inside the step in the area outside the step (the area between the pattern edge 1 and step 2 in FIG. 1). It is thinner than (the region surrounded by step 2 in FIG. 1). In other words, the area outside the step (hereinafter also referred to as “step area”) has a low light shielding ability, and thus causes noise when used as a light-shielding color filter for the solid-state imaging element. Adversely affect.

  In the present invention, the optical density (OD) is measured using the U-4100 manufactured by Hitachi High-Technologies Corporation, and the transmittance of the obtained film is measured, and the obtained transmittance (% T) is converted by the following formula 1. OD value.

  OD value = −Log (% T / 100) Equation 1

In the present invention, the optical density at the wavelength _{λ nm} is expressed as “OD _λ ”.
In the present invention, the optical density of the light-shielding color filter when it is used as the light-shielding color filter is not particularly limited as long as the above-described conditions are satisfied, but from the viewpoint of obtaining the effect of the present invention more effectively, These conditions are suitable.
That is, the [OD ₁₂₀₀ / OD ₃₆₅ ] is more preferably 0.5 or more and 2.5 or less, further preferably 0.7 or more and 2.5 or less, further preferably 1.0 or more and 2.5 or less. 3 to 2.0 is particularly preferable.
The optical density (OD ₁₂₀₀ ) at a wavelength of 1200 nm of the light-shielding color filter is preferably 2 or more, 10 or less, more preferably 2 or more and 9 or less, and further preferably 3 or more and 9 or less. It is particularly preferable that the number is 9 or less.
The optical density (OD ₃₆₅ ) at a wavelength of 365 nm of the light-shielding color filter is preferably 1 or more, 7 or less, more preferably 1 or more and 6 or less, and particularly preferably 2 or more and 6 or less.
The optical density in the wavelength region of 900 nm to 1300 nm of the light-shielding color filter is preferably 2 or more, 10 or less, more preferably 2 or more and 9 or less, still more preferably 2 or more and 8 or less, It is more preferably 3 or more and 8 or less, and particularly preferably 4 or more and 8 or less.
The ratio [OD ₉₀₀ / OD ₃₆₅ ] of the light-shielding color filter is preferably from 0.5 to 2.5, more preferably from 0.7 to 2.5, and from 1.0 to 2 Is more preferably 5 or less, and particularly preferably 1.3 or more and 2.5 or less.
The ratio [OD ₁₁₀₀ / OD ₃₆₅ ] of the light-shielding color filter is preferably from 0.4 to 2.5, more preferably from 0.6 to 2.5, and from 1.0 to 2 Is more preferably 5 or less, and particularly preferably 1.3 or more and 2.5 or less.
The ratio of the light-shielding color filter [OD ₁₃₀₀ / OD ₃₆₅ ] is preferably 0.4 or more and 2.5 or less, more preferably 0.5 or more and 2.5 or less, and 1.0 or more and 2 Is more preferably 3 or less, and particularly preferably 1.1 or more and 2.0 or less.

Hereinafter, each component of the photosensitive resin composition of this invention is demonstrated.
<Black color material>
As the black color material in the present invention, various known black pigments and black dyes can be used. In particular, from the viewpoint of realizing a high optical density with a small amount, carbon black, titanium black, iron oxide, manganese oxide, graphite Among them, carbon black and titanium black are preferable.
The photosensitive resin composition of this invention may contain only 1 type of black color materials, or may contain 2 or more types.

The average primary particle size (average primary particle size) of the black color material is preferably small from the viewpoint of foreign matter generation and the influence on the yield in the production of a solid-state imaging device. The average primary particle size is preferably 100 nm or less, more preferably 50 nm or less, and particularly preferably 30 nm or less.
The average particle diameter can be measured by applying a colorant to a suitable substrate and observing with a scanning electron microscope.

The content of the black color material in the photosensitive resin composition is not particularly limited, but is preferably as high as possible in order to obtain a high optical density in the thin film, preferably 5 to 98% by mass, 95 mass% is still more preferable, and 15-95 mass% is especially preferable.
When the black color material is 5% by mass or more, a higher optical density can be obtained even when the film thickness is thin, and when it is 98% by mass or less, photocuring is promoted more effectively and the strength of the film is improved. Development latitude can be widened.

The carbon black is black fine particles including carbon fine particles, and preferable particles include carbon fine particles having a diameter of about 3 to 1000 nm. Further, the surface of the fine particles can have functional groups containing various carbon atoms, hydrogen atoms, oxygen atoms, sulfur atoms, nitrogen atoms, halogens, inorganic atoms and the like.
Carbon black can be changed in its properties by variously changing the particle diameter (particle size), structure (particle connection), and surface properties (functional group) according to the intended application. It is also possible to change the blackness and affinity with the paint, or to provide conductivity.

  Specific examples of the carbon black include, for example, carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850 manufactured by Mitsubishi Chemical Corporation. , MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Diab N339, diamond black SH, diamond black SHA, diamond black LH, diamond black H, diamond black HA, diamond black SF, diamond black N550M, diamond black E, diamond black G, diamond black R, diamond black N760M, diamond black LP. Carbon black thermax N990, N991, N907, N908, N990, N991, N908, etc. manufactured by Cancarb;

Carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa's carbon black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2, ColorBlack Fw1, ColorBlack 170, BlackBlack, BlackBlack S160, Special Black 6, Special Black 5, Special Black 4, Special Black 4A, Printex U, Printex V, Printex 140U, Printex 140V, etc. ;

Show Black Cabot Show Black N134, Show Black N110, Show Black N234, Show Black N220, Show Black N219, Show Black N285, Show Black N339, Show Black N330, Show Black N326 Show Black N351, Show Black N330T, Show Black IP200, Show Black IP300, Show Black MAF, Show Black N500, Show Black N762;

Nihon Kasei Niteron # 300, Niteron # 200, Niteron # 200H, Niteron # 200IS, Niteron # 200L, etc .; Tokai Carbon Seast 9H, Seast 9, Seast 7HM, Seast 6, Seast 600, Seast 5H, Seast KH Seast 3H, Seast 3, Seast 300, Seast NH, Seast N, Seast 3M, Seast SVH, Seast 116HM, Seast 116, Seast SO, Seast F, Seast FM, Seast V, Seast S, etc .; Cabot VULCAN10H, VULCAN9 , VULCAN7H, VULCAN6, VULCAN6LM, REGAL300, VULCAN M, VULCAN 3H, VULCAN 4H, VULCAN J, VULCAN3, VULCAN299, STE RLING-SO, STERLING V, STERLING VH, STERLING 142, STERLING-NS, REGAL-SRF, and the like.
In addition, other products such as those manufactured by Columbian, manufactured by Engineered Carbon, and manufactured by Sid Richardson may be used.

The carbon black may preferably have an insulating property.
The carbon black having an insulating property is a carbon black exhibiting an insulating property when the volume resistance as a powder is measured by the following method. For example, an organic substance is adsorbed, coated, or coated on the surface of the carbon black particles. It means having an organic compound on the surface of carbon black particles, such as chemically bonded (grafted).
That is, carbon black was dispersed in propylene glycol monomethyl ether such that benzyl methacrylate and methacrylic acid had a molar ratio of 70:30 copolymer (mass average molecular weight 30,000) and 20:80 mass ratio. Was applied to a chrome substrate having a thickness of 1.1 mm and 10 cm × 10 cm to prepare a coating film having a dry film thickness of 3 μm, and the coating film was further heated in a hot plate at 220 ° C. for about 5 minutes. Later, a high resistivity meter manufactured by Mitsubishi Chemical Corporation conforming to JISK6911, Hirestar UP (MCP-HT450) is applied, and the volume resistance value is measured in an environment of 23 ° C. and 65% relative humidity. Carbon black having a volume resistance value of 10 ⁵ Ω · cm or more, more preferably 10 ⁶ Ω · cm or more, and particularly preferably 10 ⁷ Ω · cm or more is preferable.

  As the carbon black as described above, for example, JP-A-11-60988, JP-A-11-60989, JP-A-10-330634, JP-A-11-80583, JP-A-11-80584, Resin-coated carbon black disclosed in JP-A-9-124969 and JP-A-9-95625 can be used.

The titanium black is a black particle having a titanium atom. Preferred are low-order titanium oxide and titanium oxynitride. The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. Specifically, it can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and a water-repellent substance as disclosed in Japanese Patent Application Laid-Open No. 2007-302836. Processing is also possible.
The titanium black is a composite oxide such as Cu, Fe, Mn, V, Ni, etc., and a black pigment such as cobalt oxide, iron oxide, carbon black, aniline black, etc. for the purpose of adjusting dispersibility, colorability and the like. You may contain in a seed | species or 2 or more types of combinations, In this case, 50 mass% or more of a pigment shall occupy a titanium black particle.
In addition, for the purpose of controlling the light-shielding property at a desired wavelength, it is also possible to add existing colorants such as pigments such as red, blue, green, yellow, cyan, magenta, violet and orange, or dyes. .

  Examples of commercially available titanium black products include Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, manufactured by Mitsubishi Materials Corporation (Gemco Co., Ltd.), Alacka Chemical Co., Ltd. ) D and the like.

  The titanium black can be produced by heating a mixture of titanium dioxide and titanium metal in a reducing atmosphere for reduction (Japanese Patent Laid-Open No. 49-5432), ultrafine obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, No. 61-201610), and a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610). It is not a thing.

  The particle size of the titanium black particles is not particularly limited, but is preferably 3 to 2000 nm and more preferably 10 to 500 nm from the viewpoint of dispersibility and colorability.

The specific surface area of the titanium black is not particularly limited, but the water repellency after the surface treatment of the titanium black with a water repellent agent has a predetermined performance. 150 meters ² / g approximately, among others 20~100m about ² / g are preferred.

  In addition, a dispersant having an acid value / amine value can be used for the dispersion of the carbon black and titanium black described above. Specifically, Solsperse 24000, Solsperse 33500, Big Chemie Japan (Avicia Co., Ltd.) Disperbyk161 manufactured by Co., Ltd. can be used. Here, “having an acid value / amine value” means a dispersant having a group having an acid value, a group having an amine value, or both.

In addition, as other dispersants, a polymer obtained by polymerizing monomers such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide or a derivative thereof, styrene or a derivative thereof, or the above-mentioned monomer is used. A copolymer obtained by polymerization can be used as a dispersant.
Examples of the monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-phenylstyrene, o-chlorostyrene, m- Styrene monomers such as chlorostyrene and p-chlorostyrene; acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, stearyl acrylate, 2-acrylic acid 2- Ethylhexyl, hydroxyethyl acrylate, hydroxypropyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, methacrylate (Meth) acrylate monomers such as dodecyl acid, benzyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, ethylene, propylene, butylene, vinyl chloride, vinyl acetate, acrylonitrile Examples thereof include homopolymers or copolymers of various monomers such as acrylamide, methacrylamide, and N-vinylpyrrolidone. Of these, (meth) acrylic acid ester-based polymers are preferable.

  As other materials that can be used for dispersion, resins such as polyurethane and polyimide, and siloxane-based polymers described in JP-A Nos. 2002-241616 and 2002-234959 can also be used.

  The resin used as the dispersant is not limited in molecular weight as long as dispersibility can be ensured, but from the viewpoint of dispersibility, the weight average molecular weight is preferably 500 to 200,000, preferably 800 to 50000, more preferably 1000 to 30000. is there.

  As the dispersion medium for dispersing the black color material such as carbon black or titanium black, various water-soluble or water-insoluble materials can be used as long as they can function as a solvent for dispersion. For example, water; Alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and allyl alcohol; ethylene glycol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol, polyethylene glycol, polypropylene glycol, diethylene glycol monoethyl ether, polypropylene glycol monoethyl ether, polyethylene Glycols such as glycol monoallyl ether and polypropylene glycol monoallyl ether or derivatives thereof; glycerol, Roll monoethyl ether, glycerol or its derivatives such as glycerol monoallyl ether; ethers such as tetrahydrofuran and dioxane; ketones such as methyl ethyl ketone and methyl isobutyl ketone;

Liquid paraffin, decane, decene, methylnaphthalene, decalin, kerosene, diphenylmethane, toluene, dimethylbenzene, ethylbenzene, diethylbenzene, propylbenzene, cyclohexane, partially hydrogenated hydrocarbons such as triphenyl, polydimethylsiloxane, and partial octyl substitution Silicone oils such as polydimethylsiloxane, partially phenyl-substituted polydimethylsiloxane, fluorosilicone oil, halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, bromobenzene, chlorodiphenyl, and chlorodiphenylmethane, Dilroll (manufactured by Daikin Industries, Ltd.) , Fluorides such as demnam (Daikin Industries Co., Ltd.), ethyl benzoate, octyl benzoate, dioctyl phthalate, trioctyl trimellitic acid, sebashi Ester compounds such as dibutyl acid, ethyl (meth) acrylate, butyl (meth) acrylate, dodecyl (meth) acrylate, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacrylamide, N, Amide solvents such as N-dimethylacetamide and N-methylpyrrolidone are appropriately selected and used alone or in combination.

In preparing a dispersion of a black color material (for example, titanium black) in the present invention, 5 to 200 parts by mass, more preferably 10 to 100 parts by mass of the polymer component is added to 100 parts by mass of the black color material. Is preferred.
If the polymer component is 5 parts by mass or more, the surface property of the black color material can be kept better, and if the polymer component is 200 parts by mass or less, the inherently required black color such as light-shielding property and colorability The characteristics of the material can be further improved.

The photosensitive resin composition of the present invention may contain only one kind of the aforementioned black color material, or may contain two or more kinds. From the viewpoint of more effectively suppressing the decrease in the light shielding ability in the peripheral portion, the black color material in the present invention preferably contains titanium black.
The photosensitive resin composition of the present invention includes red, blue, green, yellow, cyan, magenta, violet, orange, etc. for the purpose of controlling the light-shielding property of a desired wavelength in addition to the black color material described above. It is also possible to add known colorants such as other pigments or dyes.
The colorant to be used in combination (combination colorant) is preferably used in the range of 2 to 50 parts by mass, more preferably the combination colorant with respect to 100 parts by mass of the total of the black colorant and the combination colorant. It is 2-30 mass parts, Most preferably, a combined colorant is 2-10 mass parts.

<Photopolymerizable compound>
The photosensitive resin composition of the present invention contains a photopolymerizable compound.
As the photopolymerizable compound, for example, an addition polymerizable compound having at least one ethylenically unsaturated double bond can be used. Specifically, at least one terminal ethylenically unsaturated bond, preferably It is selected from compounds having two or more. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and 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 epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving 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 group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH ... (A)
(However, in general formula (A), R ⁴ and R ⁵ each represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using 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, A photosensitive resin composition having an excellent photosensitive speed can be obtained.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, the Japan Adhesion Association magazine vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these photopolymerizable compounds, the details of usage, such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the final performance design of the photosensitive resin composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.
It is also photopolymerizable with respect to compatibility and dispersibility with other components (for example, photopolymerization initiators, colorants (pigments, dyes, etc.), binder polymers, etc.) contained in the photosensitive resin composition. The selection and use method of the compound is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more compounds in combination. In addition, a specific structure may be selected for the purpose of improving adhesion to a hard surface such as a support.

  The content of the photopolymerizable compound in the total solid content of the photosensitive resin composition of the present invention is not particularly limited, but the effect of the present invention can be obtained more effectively. From a viewpoint, 5-80 mass% is preferable, 10-80 mass% is more preferable, and 10-75 mass% is still more preferable. The content is preferably 15 to 75% by mass, more preferably 15 to 60% by mass, and particularly preferably 20 to 60% by mass.

<Resin>
The photosensitive resin composition of the present invention contains a resin.
It is preferable to use a linear organic polymer as the resin. As such a “linear organic polymer”, a known one can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. , JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, a resin obtained by homo- or copolymerization of a monomer having a carboxyl group, acid anhydride Resins in which acid anhydride units are hydrolyzed, half-esterified or half-amidated, or epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride, etc. It is done. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  When a copolymer is used as the resin (for example, alkali-soluble resin) in the present invention, a monomer other than the above-mentioned monomers can also be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (12).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic esters having an aliphatic hydroxyl group such as methacrylic esters.
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like can be mentioned.

  Among these, a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane binder polymers containing acid groups as described in JP 271741 and Japanese Patent Application No. 10-116232, and urethane binder polymers having acid groups and double bonds in side chains as described in JP-A No. 2002-107918 Is excellent in strength, and is advantageous in terms of printing durability and suitability for low exposure.
In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Application Laid-Open No. 2001-318463, and the like is preferable because of its excellent balance of film strength and developability.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  The resin of the present invention is preferably a resin having a polymerizable group among the resins described above. The polymerizable group is preferably a group containing a double bond, and more preferably an acryloyl group or a methacryloyl group.

The weight average molecular weight of the resin contained in the photosensitive resin composition in the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably 1, It is 000 or more, More preferably, it is the range of 2,000-250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.
These resins may be any of random polymers, block polymers, graft polymers and the like.

The resin in the present invention can be synthesized by a conventionally known method. Solvents used in the synthesis include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used when synthesizing the resin in the present invention include known compounds such as an azo initiator and a peroxide initiator.

  Although there is no limitation in particular as content (total content in the case of 2 or more) of resin in the total solid of the photosensitive resin composition of this invention, from the viewpoint of obtaining the effect of this invention more effectively. 5-50 mass% is preferable, 10-40 mass% is more preferable, 10-35 mass% is especially preferable.

<Photopolymerization initiator>
The photosensitive resin composition of the present invention contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it can polymerize the above photopolymerizable compound, but is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyl oxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone compound. And derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, oxime compounds, and the like.

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

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

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

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

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

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

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

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

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

  In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123) manufactured by Midori Chemical, T manufactured by PANCHIM Series (for example, T-OMS, T-BMP, TR, TB), Irgacure series manufactured by Ciba Specialty Chemicals (for example, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261), Darocur series (eg Darocur 1173), 4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1, 2-octanedione, 1- O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2,2- Dimethoxy-2-phenylacetophenone,

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

Among these photopolymerization initiator species, oxime photopolymerization initiators are preferable. Among the oxime photopolymerization initiators, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is preferred.
As the oxime photopolymerization initiator, a compound represented by the following general formula (1) (hereinafter also referred to as “new oxime compound”) is also preferable.

(New oxime compound)
The novel oxime compound in the present invention is a compound represented by the following general formula (1).

  In the general formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group shown below.
Examples of the monovalent nonmetallic atomic group represented by R include an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An alkynyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent An arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, and a substituent. Good phosphinoyl group, heterocyclic group which may have a substituent, alkylthiocarbonyl group which may have a substituent, arylthiocarbonyl group which may have a substituent, dialkyl which may have a substituent Aminocal Group, optionally dialkylaminothiocarbonyl group, or the like may have a substituent.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl 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, 3-nitro Enashiru group, and the like.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable, and a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , M-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, Phenalenyl, fluorenyl, anthryl, bianthracenyl, teranthraceni Group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexa Examples thereof include a phenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an oberenyl group.

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. For example, a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, and a hexylsulfinyl group. Group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methoxymethylsulfinyl group and the like.

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, such as a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfuric group Iniru group, 4-dimethylaminophenyl sulfinyl group and the like.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. For example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group. Group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, perfluoroalkylsulfonyl group, etc. It is done.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminopheny Sulfonyl group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyl. Examples thereof include an oxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  The aryloxycarbonyl group which may have a substituent includes a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenyloxycarbonyl group, and a 4-phenylsulfanylphenyloxycarbonyl group. 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3 -Chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fur B phenyloxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and 4-methoxyphenyloxycarbonyl group.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group. Group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group that 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. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl 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, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl 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 Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Examples of the alkylthiocarbonyl group which may have a substituent include, for example, a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, an octadecylthiocarbonyl group, A trifluoromethylthiocarbonyl group etc. are mentioned.

  Examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, 4-dimethyl. Aminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group Group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group Boniru group, 4-methoxyphenyl thiocarbonyl group.

  Examples of the dialkylaminocarbonyl group that may have a substituent include a dimethylaminocarbonyl group, a dimethylaminocarbonyl group, a dipropylaminocarbonyl group, and a dibutylaminocarbonyl group.

  Examples of the dialkylaminothiocarbonyl group which may have a substituent include a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group, and a dibutylaminothiocarbonyl group.

  Among them, from the viewpoint of increasing sensitivity, R is more preferably an acyl group, and specifically, an acetyl group, an ethyloyl group, a propioyl group, a benzoyl group, and a toluyl group are preferable.

Examples of the monovalent substituent represented by B include an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an arylcarbonyl group which may have a substituent, or Represents a heterocyclic carbonyl group which may have a substituent. Among them, the structure shown below is particularly preferable.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in General Formula (2), which will be described later, and preferred examples are also the same.

Examples of the divalent organic group represented by A include alkylene having 1 to 12 carbon atoms which may have a substituent, cyclohexylene which may have a substituent, and alkynylene which may have a substituent. Is mentioned.
Examples of the substituent that can be introduced into these groups include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group, p- Aryloxy groups such as tolyloxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acyloxy groups such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group Group, acyl group such as methacryloyl group, methoxalyl group, methylsulfanyl group, alkylsulfanyl group such as tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, Alkylamino groups such as hexylamino group, dimethylamino groups, diethylamino groups, morpholino groups, dialkylamino groups such as piperidino groups, phenylamino groups, arylamino groups such as p-tolylamino groups, methyl groups, ethyl groups, tert- In addition to alkyl groups such as butyl group and dodecyl group, phenyl groups, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group and the like, hydroxy group, carboxy group, formyl group, mercapto Group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfonyl group Group, triphenylphenacylphos Niumiru group, and the like.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent.
Specifically, phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 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-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, pentalenyl group, binaphthalenyl group, Turnaphthalenyl group, Quarter naphthalenyl group, Heptaenyl group, Biphenylenyl group, Indacenyl group, Fluoranthenyl group, Acenaphthylenyl group, Aceantrirenyl group, Phenalenyl group, Fluorenyl group, Anthryl group, Bianthracenyl group, Teranthracenyl group, Quarter Anthracenyl group, anthraquinolyl group, phenanthri Group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, A trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, an obalenyl group, and the like can be given. Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  When the phenyl group has a substituent, examples of the substituent include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group. Group, aryloxy group such as phenoxy group, p-tolyloxy group, methylthioxy group, ethylthioxy group, alkylthioxy group such as tert-butylthioxy group, arylthiooxy group such as phenylthioxy group, p-tolyloxy group, methoxycarbonyl Groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups, benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups, methacryloyl groups, methoxalyl groups, etc. Group, Alkylsulfanyl groups such as tilsulfanyl group, tert-butylsulfanyl group, arylsulfanyl groups such as phenylsulfanyl group, p-tolylsulfanyl group, alkylamino groups such as methylamino group, cyclohexylamino group, dimethylamino group, diethylamino group, Dialkylamino groups such as morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, alkyl groups such as ethyl group, tert-butyl group and dodecyl group, hydroxy group, carboxy group, formyl group, mercapto Group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, di Chill sulfo Niu mill group, triphenyl phenacyl phosphonium Niu mill group, and the like.

  In the general formula (1), it is preferable from the viewpoint of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure.

  The novel oxime compound in the present invention is preferably a compound represented by the following general formula (2).

  In the general formula (2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, and Ar represents an aryl group. n is an integer of 0-5.

  R, A, and Ar in the general formula (2) have the same meanings as R, A, and Ar in the general formula (1), and preferred examples thereof are also the same.

  Examples of the monovalent substituent represented by X include an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkenyl group that may have a substituent, and a substituent. An alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, and a substituent. Good arylthioxy group, acyloxy group which may have a substituent, alkylsulfanyl group which may have a substituent, arylsulfanyl group which may have a substituent, alkyl which may have a substituent A sulfinyl group, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, May have a substituent An alkoxycarbonyl group, an optionally substituted carbamoyl group, an optionally substituted sulfamoyl group, an optionally substituted amino group, an optionally substituted phosphinoyl group, and a substituent A heterocyclic group, a halogen group and the like which may have

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-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, 3-ni Rofenashiru group, and the like.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable, and a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , M-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, Phenalenyl, fluorenyl, anthryl, bianthracenyl, teranthraceni Group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexa Examples include a phenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, and an oberenyl group.

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, for example, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, or a sec-butoxy group. Tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, ethoxycarbonylmethyl group, 2 -Ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarb Methylpropenylmethyl group, N- methyl -N- benzylaminocarbonyl methyloxy group, a benzyloxy group, and a cyanomethyloxy group.

  The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group, Examples include 4-fluorophenyloxy group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, 4-phenylsulfanylphenyloxy group and the like.

  The alkylthioxy group which may have a substituent is preferably a thioalkoxy group having 1 to 30 carbon atoms. For example, a methylthioxy group, an ethylthioxy group, a propylthioxy group, an isopropylthioxy group, a butylthioxy group, an isobutylthio group. Oxy group, sec-butylthioxy group, tert-butylthioxy group, pentylthioxy group, isopentylthioxy group, hexylthioxoxy, heptylthioxy group, octylthioxy group, 2-ethylhexylthioxy group, decylthioxy group, dodecylchioxy group Examples thereof include an oxy group, an octadecylthioxy group, and a benzylthioxy group.

  The arylthioxy group which may have a substituent is preferably an arylthioxy group having 6 to 30 carbon atoms, such as a phenylthioxy group, a 1-naphthylthioxy group, a 2-naphthylthioxy group, 2 -Chlorophenylthioxy group, 2-methylphenylthioxy group, 2-methoxyphenylthioxy group, 2-butoxyphenylthioxy group, 3-chlorophenylthioxy group, 3-trifluoromethylphenylthioxy group, 3-cyano Phenylthioxy group, 3-nitrophenylthioxy group, 4-fluorophenylthioxy group, 4-cyanophenylthioxy group, 4-methoxyphenylthioxy group, 4-dimethylaminophenylthioxy group, 4-methylsulfanyl Examples thereof include a phenylthioxy group and a 4-phenylsulfanylphenylthioxy group.

  The acyloxy group which may have a substituent is preferably an acyloxy group having 2 to 20 carbon atoms, such as an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, or trifluoromethylcarbonyloxy. Group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

  The alkylsulfanyl group which may have a substituent is preferably an alkylsulfanyl group having 1 to 20 carbon atoms. For example, a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, a butylsulfanyl group, or a hexylsulfanyl group. Group, cyclohexylsulfanyl group, octylsulfanyl group, 2-ethylhexylsulfanyl group, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, methoxymethylsulfanyl group and the like.

  The arylsulfanyl group which may have a substituent is preferably an arylsulfanyl group having 6 to 30 carbon atoms, such as a phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, 2-chlorophenylsulfanyl group, 2-methylphenylsulfanyl group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group, 4-fluorophenylsulfanyl group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfuric group Aniru group, 4-dimethylamino-phenylsulfanyl group and the like.

  The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. For example, a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, and a hexylsulfinyl group. Group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methoxymethylsulfinyl group and the like.

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, such as a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfuric group Iniru group, 4-dimethylaminophenyl sulfinyl group and the like.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. For example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group. Group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group and the like.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminopheny Sulfonyl group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyl. Oxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4- Phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group Group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group , 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group and the like.

  The carbamoyl group which may have a substituent is preferably a carbamoyl group having 1 to 30 carbon atoms, for example, an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, or an N-butylcarbamoyl group. N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2- Chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenyl Carbamoyl group N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like can be mentioned.

  The sulfamoyl group which may have a substituent is preferably a sulfamoyl group having 0 to 30 carbon atoms, for example, a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, N, N- Examples thereof include a dialkylsulfamoyl group, an N, N-diarylsulfamoyl group, and an N-alkyl-N-arylsulfamoyl group. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like.

The amino group which may have a substituent is preferably an amino group having 0 to 50 carbon atoms in total, for example, —NH ₂ , N-alkylamino group, N-arylamino group, N-acylamino group, N— Examples include sulfonylamino group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group and the like. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-tert-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenyla Group, N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino Group, N-4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenyl Amino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) Amino group, N, N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group, morpholino group, 3, - dimethyl morpholino group, and a carbazolyl group.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group. Group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group that 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. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl 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, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl 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 Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Examples of the halogen group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Furthermore, the alkyl group which may have a substituent mentioned above, the aryl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, a substituent An alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylthioxy group that may have a substituent, an arylthioxy group that may have a substituent, and a substituent. An acyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, an arylsulfanyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, and a substituent. Good arylsulfinyl group, alkylsulfonyl group which may have a substituent, arylsulfonyl group which may have a substituent, acyl group which may have a substituent, alkoxycarbonyl which may have a substituent Base The carbamoyl group which may have a substituent, the sulfamoyl group which may have a substituent, the amino group which may have a substituent, and the heterocyclic group which may have a substituent may be further substituted. It may be substituted with a group.

  Examples of such a substituent include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group and p-tolyloxy group. Aryloxy group, alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acyloxy group such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group , Acyl group such as methoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, cyclohexyl Alkylamino group such as mino group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, arylamino group such as phenylamino group, p-tolylamino group, methyl group, ethyl group, tert-butyl group In addition to alkyl groups such as dodecyl group, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, etc., hydroxy groups, carboxy groups, formyl groups, mercapto groups, Sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfonyl group, Triphenylphenacylphosphoniumyl group And the like.

Among these, X has an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy which may have a substituent A group, an arylthioxy group which may have a substituent, and an amino group which may have a substituent are preferable.
Moreover, although n in General formula (2) represents the integer of 0-5, the integer of 0-2 is preferable.

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

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

  The novel oxime compound in the present invention is preferably a compound represented by the following general formula (3).

  In the general formula (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 0-5.

  R, X, A, Ar, and n in the general formula (3) have the same meanings as R, X, A, Ar, and n in the general formula (2), and preferred examples are also the same.

  Hereinafter, although the specific example of the novel oxime compound in this invention is shown below, this invention is not limited to these.

The novel oxime compound in the present invention has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm. More preferably, a material having an absorption wavelength in a wavelength region of 360 nm to 480 nm can be exemplified. In particular, those having high absorbance at 365 nm and 405 nm are preferable.
Thus, the novel oxime compound has absorption in a long wavelength region as compared with the conventional oxime compound. Therefore, when exposed with a light source of 365 nm or 405 nm, excellent sensitivity is exhibited.

In the novel oxime compound in the present invention, the molar extinction coefficient at 365 nm or 405 nm is preferably 10,000 to 300,000, more preferably 15,000 to 300,000, from 20000 to 200,000, from the viewpoint of sensitivity. Particularly preferred.
Here, the molar extinction coefficient of the novel oxime compound was measured with a UV-visible spectrophotometer (Carry-5 spectrophotometer manufactured by Varian) at a concentration of 0.01 g / L using an ethyl acetate solvent.

  The novel oxime compound in the present invention can be synthesized, for example, by the method shown below, but is not limited to this method.

Content of the novel oxime compound in the photosensitive resin composition of this invention is 0.1-30 mass% in the total solid of the photosensitive resin composition, 1-25 mass% is more preferable, 2-20 Mass% is particularly preferred.
A novel oxime compound may be used individually by 1 type, and may use 2 or more types together.

  The novel oxime compound in the present invention has a function as a photopolymerization initiator that is decomposed by light and initiates and accelerates polymerization of the photopolymerizable compound. In particular, the novel oxime compound has excellent sensitivity to a 365 nm or 405 nm light source.

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

In addition to the above-mentioned photopolymerization initiator, other known initiators can be used for the photosensitive resin composition of the present invention.
Specifically, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Substituted α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,722,512 Aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367. Triarylimidazole dimer / p-aminophenyl ketone combination, benzothiazole compound / trihalome disclosed in Japanese Patent Publication No. 51-48516 Examples thereof include a teal-s-triazine compound.

The photosensitive resin composition of the present invention may contain only one kind of photopolymerization initiator or two or more kinds.
From the viewpoint of obtaining the effect of the present invention more effectively, the content of the photopolymerization initiator in the total solid content of the photosensitive resin composition of the present invention (total content in the case of two or more) is 3 to 3. 20 mass% is preferable, 4-19 mass% is more preferable, and 5-18 mass% is especially preferable.

<Solvent>
The photosensitive resin composition of the present invention contains a solvent.
Examples of the solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone. , Diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene Recall monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, ethyl lactate and so on.
These solvents can be used alone or in combination. It is preferable that the density | concentration of solid content with respect to a solvent is 2-60 mass%.

<Other ingredients>
(Sensitizer)
The photosensitive resin composition of the present invention may contain a sensitizer.
As the sensitizer, one that sensitizes the above-described photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism is preferable.

Examples of the sensitizer include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
That is, for example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), Thioxanthones (isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, Toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squaryu (Eg, squalium), acridine orange, coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes Carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, etc. Examples include aromatic ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.

  When the photosensitive resin composition of the present invention contains a sensitizer, the content of the sensitizer in the photosensitive resin composition is calculated in terms of solid content from the viewpoint of light absorption efficiency to the deep part and starting decomposition efficiency. 0.1 to 20% by mass is preferable, and 0.5 to 15% by mass is more preferable.

(Co-sensitizer)
The photosensitive resin composition of the present invention may contain a co-sensitizer.
The co-sensitizer has functions such as further improving the sensitivity of the photopolymerization initiator and the sensitizer to actinic radiation or suppressing inhibition of polymerization of the photopolymerizable compound by oxygen.

  Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  When the photosensitive resin composition of the present invention contains a co-sensitizer, the content of the co-sensitizer is selected from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. The range of 0.1 to 30% by mass is preferable, the range of 1 to 25% by mass is more preferable, and the range of 0.5 to 20% by mass is more preferable.

(Thermal polymerization inhibitor)
In the photosensitive resin composition of the present invention, a small amount of a thermal polymerization inhibitor can be added during production or storage of the composition in order to prevent unnecessary thermal polymerization of the photopolymerizable compound.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

When the photosensitive resin composition of the present invention contains a thermal polymerization inhibitor, the addition amount of the thermal polymerization inhibitor is preferably about 0.01 to about 5% by mass with respect to the total solid content of the photosensitive resin composition.
If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and may be unevenly distributed on the surface of the coating film during the drying process after coating. . The amount of the higher fatty acid derivative added is preferably from about 0.5 to about 10% by weight of the total composition.

(Adhesion improver)
In the photosensitive resin composition of this invention, in order to improve adhesiveness with hard surfaces, such as a support body, an adhesive improvement agent can be added. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane is most preferable.

  When the photosensitive resin composition of the present invention contains an adhesion improver, the addition amount of the adhesion improver is preferably 0.5 to 30% by mass in the total solid content of the photosensitive resin composition, and 0.7 to 20 The mass% is more preferable.

(Other additives)
Furthermore, in order to improve the physical properties of the cured film, known additives such as inorganic fillers, plasticizers, and sensitizers may be added to the photosensitive resin composition of the present invention.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. , 10% by mass or less can be added to the total mass of the photopolymerizable compound and the resin.

≪Light-shielding color filter≫
The light-shielding color filter of the present invention is formed using the above-described photosensitive resin composition of the present invention. That is, the ratio [OD ₁₂₀₀ / OD ₃₆₅ ] of the optical density (OD ₁₂₀₀ ) at a wavelength of ₁₂₀₀ nm to the optical density (OD ₃₆₅ ) at a wavelength of 365 nm is 0.5 or more and 3 or less.
With the light-shielding color filter having the above-described configuration according to the present invention, it is possible to suppress a phenomenon in which a region (step) in which the film thickness is thinner than the central part occurs in the peripheral part of the light-shielding color filter. Performance can be improved.
Here, [OD ₁₂₀₀ / OD ₃₆₅ ] is as described in the above description of the photosensitive resin composition of the present invention, and the same applies to the preferred range.
The optical density of the light-shielding color filter of the present invention in the wavelength region of 900 nm to 1300 nm is preferably 2 or more, 10 or less, more preferably 2 or more and 9 or less, and more preferably 2 or more and 8 or less. Particularly preferred. The optical density is further preferably 3 or more and 8 or less, and particularly preferably 4 or more and 8 or less.
In addition, the optical density of the light-shielding color filter of the present invention is as described in the above description of the photosensitive resin composition of the present invention, and the same applies to the preferred range.

The film thickness of the light-shielding color filter is not particularly limited, but is preferably 0.1 μm to 10 μm, more preferably 0.3 μm to 5.0 μm, from the viewpoint of more effectively obtaining the effects of the present invention. 5 μm to 3.0 μm is particularly preferable.
The size (length of one side) of the light-shielding color filter is not particularly limited, but is preferably 50 μm or more, more preferably 100 μm or more, and particularly preferably 200 μm or more from the viewpoint of obtaining the effect of the present invention more effectively. . Further, the size is preferably 500 μm or more, particularly preferably 1000 μm or more. The upper limit of the size is not particularly limited but is preferably 3000 μm.
Further, the area of the light-shielding color filter is not particularly limited, but from the viewpoint of obtaining the effect of the present invention more effectively, 0.0025 mm ² or more is more preferable, 0.01 mm ² or more is more preferable, and 0. 04 mm ² or more is particularly preferable. The area is more, more preferably 0.05 mm ² or more, more preferably 0.2 mm ² or more, 1 mm ² or more is particularly preferable. The upper limit is not particularly limited, but 9 mm ² is preferable.

  The light-shielding color filter of the present invention can be suitably used for, for example, a solid-state image sensor such as a CCD or CMOS, and is particularly suitable for a solid-state image sensor such as a CCD or CMOS having more than 1 million pixels.

≪Method for manufacturing light-shielding color filter≫
The method for forming the light-shielding color filter of the present invention described above is not particularly limited. For example, the photosensitive resin composition of the present invention described above is coated on a support, exposed through a mask, and developed. A method comprising a step of forming a pattern (hereinafter also referred to as “a method for producing a light-shielding color filter of the present invention”) is suitable.
That is, the method for producing a light-shielding color filter of the present invention comprises a step of applying a photosensitive resin composition of the present invention on a support to form a photosensitive layer (hereinafter, abbreviated as “photosensitive layer forming step” as appropriate). ), A step of exposing the photosensitive layer through a mask (hereinafter referred to as “exposure step” where appropriate), and a step of developing the exposed photosensitive layer to form a pattern (hereinafter referred to as “development step” as appropriate). And abbreviated as “)”.
Hereinafter, each process in the manufacturing method of the light-shielding color filter of this invention is demonstrated.

<Photosensitive layer forming step>
In the photosensitive layer forming step, the photosensitive resin composition of the present invention is applied on a support to form a photosensitive layer.

Examples of the support that can be used in this step include a photoelectric conversion element substrate used for a solid-state imaging element or the like, such as a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  As a coating method of the photosensitive resin composition of the present invention on the support, 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. .

  When manufacturing a light-shielding color filter, the coating thickness of the photosensitive resin composition is preferably 0.35 μm to 3.0 μm, more preferably 0.50 μm to 2.5 μm from the viewpoint of resolution and developability. preferable.

  The photosensitive resin composition coated on the support is usually dried at 70 ° C. to 130 ° C. (more preferably 70 ° C. to 110 ° C.) for 2 minutes to 4 minutes to form a photosensitive layer. The

<Exposure process>
In the exposure step, the photosensitive layer formed in the photosensitive layer forming step is exposed and cured (in the case of exposing through a mask, only the coating film portion irradiated with light is cured).
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are preferably used, and a high-pressure mercury lamp is more preferable. The irradiation intensity is preferably 5 mJ to 1500 mJ, more preferably 10 mJ to 1000 mJ, and most preferably 10 mJ to 800 mJ.

<Development process>
Subsequent to the exposure step, an alkali development treatment (development step) may be performed.
In the development step, the non-light-irradiated part in the exposure step is eluted in the alkaline aqueous solution. Thereby, only the photocured part remains.
As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 240 seconds (more preferably 20 to 90 seconds).

  Examples of the alkali used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0. An alkaline aqueous solution obtained by diluting an organic alkaline compound such as] -7-undecene with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

  In the method for producing a light-shielding color filter of the present invention, after the photosensitive layer forming step, the exposure step, and the development step are performed, the formed pattern is cured by heating and / or exposure as necessary. A curing step may be included.

≪Solid-state imaging device≫
The solid-state imaging device of the present invention includes the above-described light-shielding color filter of the present invention.
Since the solid-state imaging device of the present invention includes the light-shielding color filter of the present invention in which a decrease in light-shielding ability at the peripheral portion is suppressed, noise can be reduced and color reproducibility can be improved. .
The configuration of the solid-state imaging device of the present invention is a configuration provided with the light-shielding color filter of the present invention, and is not particularly limited as long as the configuration functions as a solid-state imaging device. The present invention has a light receiving element composed of a plurality of photodiodes and polysilicon forming a light receiving area of an image pickup element (CCD image sensor, CMOS image sensor, etc.), and the present invention is provided on the surface opposite to the light receiving element forming surface of the support. The light-shielding color filter is provided.

  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.

[Example 1]
A light-shielding color filter was formed using various photosensitive resin compositions, and the width of the step region was measured. This will be described in detail below.

<< Preparation of photosensitive resin composition >>
<Preparation of Sample 1 (photosensitive resin composition using titanium black)>
(Preparation of titanium black dispersion)
The dispersion of titanium black was subjected to a high viscosity dispersion treatment with the following composition using two rolls. The viscosity of the dispersion at this time was 40,000 mPa · s.
In addition, you may knead | mix for 30 minutes with a kneader before a high-viscosity dispersion process.

-Titanium black dispersion composition-
-Gemco Co., Ltd. titanium black 13M-T ... 40 parts-Propylene glycol monomethyl acetate solution of benzyl (meth) acrylate / (meth) acrylic acid copolymer (BzMA / MAA = 70/30, Mw: 30000, solid content 40 (Mass%) ... 6 parts · Solpers 5000 (manufactured by Zeneca) ... 1 part

The following component (A) was added to the obtained dispersion and stirred for 3 hours using a homogenizer at 3000 rpm. The obtained mixed solution was subjected to a dispersion treatment for 4 hours with a disperser using 0.3 mm zirconia beads (manufactured by Dispermat GETZMANN) to obtain a titanium black dispersion.
The viscosity of this dispersion was 8.0 mPa · s.

~ Ingredient (A) ~
・ Propylene glycol monomethyl acetate solution of benzyl (meth) acrylate / (meth) acrylic acid copolymer (BzMA / MAA = 70/30, Mw: 30000, solid content 40% by mass)… 10 parts • Propylene glycol monomethyl ether acetate… 140 parts

(Preparation of photosensitive resin composition)
The following components were mixed to obtain a photosensitive resin composition (Sample 1).
-Composition of photosensitive resin composition (Sample 1)-
-Copolymer (resin; the following compound J-1 (weight average molecular weight (Mw) 14000))
... 6.1 parts dipentaerythritol hexaacrylate (polymerizable compound; the following compound T-1)
4.8 parts ethoxylated pentaerythritol tetraacrylate (polymerizable compound; compound T-2 below) 1.7 parts titanium titanium dispersion prepared above 67 parts propylene glycol monomethyl ether acetate (PGMEA) 15.7 parts oxime photopolymerization initiator (the following compound K-1): 1.7 parts

<Preparation of sample 2 (photosensitive resin composition using carbon black)>
(Preparation of carbon black dispersion)
The dispersion of carbon black was subjected to a high viscosity dispersion treatment with two rolls having the following composition. The viscosity of the dispersion at this time was 70000 mPa · s.
In addition, you may knead | mix for 30 minutes with a kneader before a high-viscosity dispersion process.

~ Carbon black dispersion composition ~
・ Average primary particle size 15 nm carbon black: 40 parts ・ Propylene glycol monomethyl acetate solution of benzyl (meth) acrylate / (meth) acrylic acid copolymer (BzMA / MAA = 70/30, Mw: 30000, solid content: 40 mass% ) ... 8 parts · Solpers 5000 (manufactured by Zeneca) ... 2 parts

The following component (B) was added to the obtained dispersion and stirred for 3 hours using a homogenizer at 3000 rpm. The obtained mixed solution was subjected to a dispersion treatment for 4 hours with a disperser (dispar mat GETZMANN) using 0.3 mm zirconia beads to obtain a carbon black dispersion.
The viscosity of this dispersion was 40.0 mPa · s.

~ Ingredient (B) ~
・ Propylene glycol monomethyl acetate solution of benzyl (meth) acrylate / (meth) acrylic acid copolymer (BzMA / MAA = 70/30, Mw: 30000, solid content 40 mass%)… 25 parts ・ Propylene glycol monomethyl ether acetate… 125 parts

(Preparation of photosensitive resin composition)
The following components were mixed to obtain a photosensitive resin composition (Sample 2).
-Composition of photosensitive resin composition (sample 2)-
Copolymer (compound J-1): 6.1 parts Dipentaerythritol hexaacrylate (compound T-1) 4.8 parts Ethoxylated pentaerythritol tetraacrylate (compound T-2)
1.7 parts Carbon black dispersion prepared above 67 parts propylene glycol monomethyl ether acetate (PGMEA) 15.7 parts oxime photopolymerization initiator (compound K-1 above) 1.7 parts

<Preparation of sample 3 (photosensitive resin composition using titanium black)>
Sample 3 was prepared in the same manner as Sample 1 except that the same amount of the following triazine photopolymerization initiator (the following compound (VI)) was used instead of the oxime photopolymerization initiator in the preparation of Sample 1.

<Preparation of Sample 4 (photosensitive resin composition using titanium black)>
Sample 4 was prepared in the same manner as Sample 1 except that the same amount of aminoalkylphenone photopolymerization initiator (Irgacure 369 below) was used instead of the oxime photopolymerization initiator in the preparation of Sample 1.

<Preparation of sample 5 (photosensitive resin composition using titanium black)>
In the preparation of Sample 1, Sample 5 was prepared in the same manner as Sample 1 except that the same amount of Compound J-2 (resin; weight average molecular weight (Mw) 30000) was used instead of Compound J-1 (resin). Produced.

<Preparation of sample 6 (photosensitive resin composition using titanium black)>
Sample 6 was prepared in the same manner as Sample 1 except that titanium black powder (Tilack D fine particle type) manufactured by Ako Kasei Co., Ltd. was used instead of 13M-T.

<Preparation of sample 7 (photosensitive resin composition using titanium black)>
Sample 7 was prepared in the same manner as Sample 1 except that titanium black powder (Tilack D ultrafine particle type) manufactured by Ako Kasei Co., Ltd. was used instead of 13M-T.

≪Production and evaluation of shading color filter≫
The photosensitive resin composition obtained above was applied to a silicon wafer by spin coating, and then heated on a hot plate at 120 ° C. for 2 minutes to obtain a photosensitive layer.
Next, the obtained photosensitive layer was exposed at an exposure amount of 500 mJ / cm ² through a photomask having a 3 mm square pattern using an i-line stepper.
The exposed photosensitive layer was subjected to paddle development at 23 ° C. for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide. Thereafter, it was rinsed with a spin shower and further washed with pure water to obtain a light-shielding color filter.
The resulting light-shielding color filter, using Hitachi High-Technologies Ltd. U-4100, were respectively measured optical density _{(OD 365)} in the optical density _{(OD 1200)} and wavelength 365nm at a wavelength of 1200 nm, _{[OD 1200} / OD ₃₆₅ ] was calculated. Further, similarly, the optical density (OD ₁₁₀₀ ) at a wavelength of ₁₁₀₀ nm and the optical density (OD ₉₀₀ ) at a wavelength of 900 nm were measured, and [OD ₁₁₀₀ / OD ₃₆₅ ] and [OD ₉₀₀ / OD ₃₆₅ ] were calculated. Table 1 shows the calculated [OD ₁₂₀₀ / OD ₃₆₅ ], [OD ₁₁₀₀ / OD ₃₆₅ ], and [OD ₉₀₀ / OD ₃₆₅ ]. Furthermore, OD values at wavelengths of 900 nm to 1300 nm were measured. The measurement results are shown in Table 1.

Next, the obtained light-shielding color filter was photographed with an optical microscope (magnification 100 times), and the width of the step region was measured. It shows that the narrower the width of the step region, the better the light shielding ability of the central part and the peripheral part.
The measurement results for Samples 1 to 7 of the photosensitive resin composition are shown in Table 1 below.

  In Table 1, symbols such as “T-1” indicate the aforementioned compound T-1 and the like. Moreover, content of a photoinitiator shows content (mass%) in the total solid of the photosensitive resin composition. The same applies to Tables 2 and 3 described later.

As shown in Table 1, in the light-shielding color filter of the present invention having [OD ₁₂₀₀ / OD ₃₆₅ ] of 0.5 or more and 3 or less, the width of the step region was suppressed. Above all, from the comparison of Sample 1, Sample 3 and Sample 4, when an oxime photopolymerization initiator is used, and from the comparison between Sample 1 and Sample 5, the resin having a polymerizable group is used. In addition, the width of the step region is more significantly suppressed.

[Example 2]
In Example 1, in the production of Sample 1, the content of the photopolymerization initiator in the total solid content of the photosensitive resin composition was changed as shown in Table 2 below, and Samples 11 to 20 were produced. Using the obtained Sample 11 to Sample 20, a light-shielding color filter was formed in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 2.

  As shown in Table 2, when the content of the photopolymerization initiator in the total solid content of the photosensitive resin composition was 3 to 20% by mass, the width of the step region was more significantly suppressed.

Example 3
In the preparation of Sample 1, Sample 11, and Sample 20 in Example 2, the same procedure was performed except that the oxime initiator was changed from K-1 to the following compounds K-2, K-3, and K-4. Thus, samples shown in Table 3 were prepared (Sample 1-2, Sample 1-3, Sample 1-4, Sample 11-2, Sample 11-3, Sample 11-4, Sample 20-2, Sample 20- 3, Sample 20-4).
Using each of the obtained samples, a light-shielding color filter was formed in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 3.

  As shown in Table 3, it can be seen that the sample using the novel oxime-based initiator K-4 has a narrow step region.

Example 4
<< Preparation of photosensitive resin composition >>
<Preparation of Sample 31 (Photosensitive Resin Composition Using Titanium Black)>
(Preparation of titanium black dispersion)
The mixed solution having the following composition was subjected to dispersion treatment using an ultra apex mill manufactured by Kotobuki Industries Co., Ltd. as a dispersing device (bead mill).
~composition~
-Gemco Co., Ltd. Titanium Black 13M-T ... 300 parts-DISPERBYK180 (Bicchemy Japan Co., Ltd.) ... 200 parts-Propylene glycol monomethyl ether acetate ... 600 parts

At this time, the dispersing apparatus was operated under the following conditions.
・ Bead diameter: φ0.05mm
・ Bead filling rate: 75% by volume
・ Peripheral speed: 8m / sec
・ Pump supply amount: 10kg / hour
・ Cooling water: Tap water ・ Bead mill annular passage volume: 0.15L
・ Amount of liquid mixture to be dispersed: 1.1 kg
・ Dispersion time: 8 hours

(Preparation of photosensitive resin composition)
The following components were mixed to obtain a photosensitive resin composition (Sample 31).
-Composition of photosensitive resin composition (sample 31)-
· Titanium black dispersion prepared above · · 40 parts · Dipentaerythritol hexaacrylate (compound T-1) · · 7 parts · Oxime photopolymerization initiator (compound K-1) · 5 parts · Resin (compound J-1) ... 7 parts · Propylene glycol monomethyl ether acetate ... 30 parts

<Production of Sample 32 to Sample 39 (Photosensitive Resin Composition Using Titanium Black)>
In the preparation of Sample 31, Samples 32 to 39 were prepared in the same manner as the preparation of Sample 31 except that the photopolymerization initiator and the resin were changed as shown in Table 4 below.

≪Production and evaluation of shading color filter≫
Using each sample (sample 31 to sample 39) obtained above, a light-shielding color filter was formed in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 4 below.

  As shown in Table 4, the width of the step region of the light-shielding color filter produced using Sample 31 to Sample 39 was suppressed.

As mentioned above, although the Example at the time of using a specific compound was demonstrated as a black color material, a photopolymerizable compound, resin, a photoinitiator, and a solvent, also when using compounds other than the above, light-shielding color As long as the ratio [OD ₁₂₀₀ / OD ₃₆₅ ] in the filter satisfies 0.5 or more and 3 or less, the same effect as described above can be obtained.
In the above embodiment, the light-shielding color filter is formed on the silicon wafer. However, the silicon wafer is changed to a solid-state image sensor substrate on which a light receiving element such as a photodiode is formed, and the opposite side of the light receiving element forming surface. By forming a light-shielding color filter (on the back side), a solid-state imaging device with less noise and excellent color reproducibility can be produced.

1 Pattern edge 2 Step 10 Light blocking color filter

Claims (10)

When at least a black color material, a photopolymerizable compound, a resin, a photopolymerization initiator, and a solvent are used to form a light-shielding color filter, an optical density (OD ₁₂₀₀ ) at a wavelength of ₁₂₀₀ nm and an optical density (OD ₃₆₅ ) at a wavelength of 365 nm The ratio [OD ₁₂₀₀ / OD ₃₆₅ ] of the photosensitive resin composition is 0.5 or more and 3 or less.   2. The photosensitive resin composition according to claim 1, wherein when the light-shielding color filter is used, an optical density in a wavelength region of 900 nm to 1300 nm is 2 or more and 10 or less.   The photosensitive resin composition according to claim 1, wherein the black color material contains titanium black.   The said photoinitiator contains an oxime type photoinitiator, The photosensitive resin composition of any one of Claims 1-3 characterized by the above-mentioned.   It is used for formation of the light-shielding color filter for solid-state image sensors, The photosensitive resin composition of any one of Claims 1-4 characterized by the above-mentioned.   6. The photosensitive resin composition according to claim 1, wherein the content of the photopolymerization initiator in the total solid content is 3% by mass or more and 20% by mass or less. . A ratio of an optical density (OD ₁₂₀₀ ) at a wavelength of ₁₂₀₀ nm and an optical density (OD ₃₆₅ ) at a wavelength of 365 nm formed using the photosensitive resin composition according to any one of claims 1 to 6 [OD ₁₂₀₀ / OD ₃₆₅ ] is 0.5 or more and 3 or less.   The light-shielding color filter according to claim 7, wherein an optical density in a wavelength region of 900 nm to 1300 nm is 2 or more and 10 or less.   A light-shielding property comprising a step of forming a pattern by applying the photosensitive resin composition according to any one of claims 1 to 6 on a support, exposing through a mask, and developing the photosensitive resin composition. A method for producing a color filter.   A solid-state imaging device comprising the light-shielding color filter according to claim 7.