JP2009244401A - Black photosensitive resin composition for solid state image sensor and method of forming image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a black photosensitive resin composition for a solid state image sensor in which a small amount of a residue is generated, adhesion to a substrate after being exposed is excellent and a black pattern having an excellent rectangular cross section profile is obtained. <P>SOLUTION: The black photosensitive resin composition for the solid state image sensor contains at least: a color material for black; a photopolymerization compound; and a photopolymerization initiator wherein the solution rate of a non-exposed region when being developed at 23 °C by using a developer having pH (23 °C) of 8 to 12 containing 0.1 mass% of a tetramethylammonium hydroxide, and a nonionic surfactant is ≥0.005 μm/sec and ≤0.060 μm/sec. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a black photosensitive resin composition for a solid-state imaging device, which is colored black, and an image forming method.

  A solid-state imaging device such as a CCD or CMOS is provided with a light-shielding film for the purpose of preventing noise and improving image quality. For the formation of the light shielding film, a photosensitive resin composition containing a black color material such as carbon black or titanium black is widely used.

  As a photosensitive resin composition used for forming a light-shielding film for a solid-state imaging device (which can also be referred to as a black pattern, a light-shielding color filter, or a light-shielding filter), it sufficiently shields incident light in the visible range. There is a need for a black resist that can be used. In order to impart sufficient light shielding properties with the resist material, it is necessary to increase the content of the color material, which is the light shielding material, or to increase the film thickness. For this reason, the optical density of the film itself is increased, and for example, when exposure is performed with a light source such as i-line and patterning, light does not reach the deep part of the film, and photocuring may not proceed sufficiently. In such a case, the pattern is over-developed in the deep part of the film and the pattern is thinned, or the adhesion of the pattern formed on the wafer in the subsequent development is poor and peels off from the wafer.

In connection with such a phenomenon, a benzophenone compound having a specific structure as a blue color resist having a low light transmittance at an exposure wavelength of 365 nm such as i-line used for exposure of a photosensitive resin composition for a solid-state imaging device, has started. A photosensitive resin composition in which an O-acyloxime compound or a halomethyltriazine compound and an acetophenone compound are combined as an agent is disclosed, and it is said that the sensitivity can be increased (see, for example, Patent Documents 1 and 2). ).
JP 2003-96118 A JP 2003-313217 A

  However, the light-shielding black pattern of the color filter for the solid-state imaging device has a lower light transmittance at an exposure wavelength of 365 nm than that of red (R), green (G), and blue (B). Even if it is devised to adjust the exposure sensitivity in terms of the resist composition such as a photosensitive resin composition in which specific components are combined, a good pattern cannot be formed.

  In recent years, particularly in color filters for solid-state imaging devices, the coloring pattern is made thinner (for example, 1 μm or less in thickness) and the pixel pattern size is reduced to 2 μm or less (for example, 0.5 to 2.0 μm). As a solid-state imaging device application, a technique that can reduce the thickness of the light-shielding film is also demanded.

  The present invention has been made in view of the above, and has a black development resin composition for a solid-state imaging device that has a small development residue, excellent adhesion to a substrate after exposure, and a black pattern having a good rectangular cross-sectional profile. An image forming method capable of forming a black pattern with high substrate adhesion by preventing reverse development of the cross-sectional profile of the pattern while preventing development residue and achieving the object. This is the issue.

  The present invention pays attention to the developability of the unirradiated region of the photosensitive resin composition, and in the unirradiated region, by adjusting to the side where the development speed is rather delayed, the film of the exposed region where the progress of the curing reaction is insufficient. The inventors have obtained knowledge that over-development in the deep part, that is, the pattern lower film part close to the substrate is suppressed, and that the pattern shape and the substrate adhesion can be improved, and have been achieved based on such knowledge. In particular, it is effective when the black density is high (for example, the optical density when the film is formed at 1.0 μm is 3.5 or more) and when the content of the photopolymerizable compound is small.

Specific means for achieving the above object are as follows.
<1> A pH (23 ° C.) of 8 to 12 containing at least black colorant, a photopolymerizable compound, and a photopolymerization initiator, and containing 0.1% by mass of tetramethylammonium hydroxide and a nonionic surfactant. It is a black photosensitive resin composition for a solid-state imaging device having a dissolution rate of a non-light-irradiated region when it is developed at 23 ° C. using a developer solution of 0.005 μm / sec or more and 0.060 μm / sec or less.
<2> The black photosensitive resin composition for a solid-state imaging device according to <1>, wherein the optical density (OD) at a wavelength of 365 nm when the film is 1.0 μm thick is 3.5 or more It is a thing.

<3> The black photosensitive resin composition for a solid-state imaging device according to <1> or <2>, wherein the black color material is at least one of carbon black and titanium black.
<4> The black photosensitive resin composition for a solid-state imaging device according to any one of <1> to <3>, wherein the photopolymerization initiator is an oxime initiator. .
<5> At least one of the photopolymerizable compounds is a bifunctional or higher (meth) acrylate monomer, and the content of the photopolymerizable compound in the black photosensitive resin composition is the total solid content of the composition. It is 5-20 mass% with respect to this, It is a black photosensitive resin composition for solid-state image sensors as described in any one of said <1>-<4> characterized by the above-mentioned.

<6> A film formed of a black photosensitive resin composition containing at least a black colorant, a photopolymerizable compound, and a photopolymerization initiator is irradiated with light, and then the light of the film is not irradiated using a developer. This is an image forming method for forming a black pattern for a solid-state imaging device by dissolving an irradiation region at a dissolution rate of 0.005 μm / sec or more and 0.060 μm / sec or less.
<7> The image according to <6>, wherein the developer contains 0.1% by mass of tetramethylammonium hydroxide and a nonionic surfactant and has a pH (23 ° C.) of 8 to 12. It is a forming method.

<8> The image forming method according to <6> or <7>, wherein the optical density (OD) of the film at a wavelength of 365 nm is 3.5 or more.
<9> At least one of the photopolymerizable compounds is a bifunctional or higher (meth) acrylate monomer, and the content of the photopolymerizable compound in the black photosensitive resin composition is a black photosensitive resin composition. The image forming method according to any one of <6> to <8>, wherein the content is 5 to 20% by mass with respect to the total solid content.

According to the present invention, it is possible to provide a black photosensitive resin composition for a solid-state imaging device that has a small amount of development residue, excellent adhesion to a substrate after exposure, and a black pattern having a good rectangular cross-sectional profile. Also,
According to the present invention, it is possible to provide an image forming method capable of forming a black pattern with high substrate adhesion by preventing reverse development of the cross-sectional profile of a pattern while preventing development residue.

  Hereinafter, the black photosensitive resin composition for a solid-state imaging device of the present invention and an image forming method using the same will be described in detail.

<Black photosensitive resin composition for solid-state image sensor>
The black photosensitive resin composition for a solid-state imaging device of the present invention is a black photosensitive resin composition used for forming a light-shielding film constituting a solid-state imaging device or a color filter thereof, and at least a black colorant and a photopolymerizable property. Light rays when developed at 23 ° C. using a developer having a pH (23 ° C.) of 8 to 12 containing 0.1% by mass of tetramethylammonium hydroxide and a nonionic surfactant containing a compound and a photopolymerization initiator The dissolution rate of the unirradiated region is configured to be 0.005 μm / sec or more and 0.060 μm / sec or less. In addition, the black photosensitive resin composition for a solid-state imaging device of the present invention is generally configured using a solvent, and further can be configured using other components such as a sensitizer as necessary.

  In the black photosensitive resin composition for a solid-state imaging device of the present invention (hereinafter sometimes simply referred to as “photosensitive resin composition”), dissolution when an unexposed area is developed under specific development conditions. When the speed is 0.005 to 0.060 μm / sec, it is possible to perform development while suppressing the development speed in the light non-irradiated region, and the vicinity of the light non-irradiated region that is dissolved and removed in the developer relatively quickly. In this exposure area, it is possible to suppress dissolution of the deep part of the film where the progress of the curing reaction is insufficient, that is, the pattern lower film part close to the substrate, that is, over-development. While preventing occurrence, reverse taper of the pattern is avoided, a rectangular pattern having a good cross-sectional profile is obtained, and the substrate adhesion of the pattern is also improved.

  The black photosensitive resin composition for a solid-state imaging device of the present invention is at 23 ° C. using a developer having a pH (23 ° C.) of 8 to 12 containing 0.1% by mass of tetramethylammonium hydroxide and a nonionic surfactant. The dissolution rate of the non-irradiated region when developed is in the range of 0.005 to 0.060 μm / sec. When the dissolution rate is within this range, reverse cross-tapering of the cross-sectional profile of the pattern is prevented, a good rectangular black pattern is obtained, and the adhesion with the substrate is also improved. Thereby, a high-resolution light-shielding pattern can be obtained, and the occurrence of pattern peeling can be prevented.

In other words, the dissolution rate of the non-irradiated region is not only longer than 0.005 μm / sec but also requires a long time for development, and a development residue is likely to occur, and when it exceeds 0.060 μm / sec, Overdevelopment occurs in the deep part of the film in the exposed area, specifically the lower film part close to the substrate of the film, and the cross-sectional profile of the formed pattern becomes a reverse taper shape, resulting in a good rectangular pattern after development. In other words, the substrate adhesion also decreases.
In particular, when the black density is high, the light transmittance upon irradiation (for example, the light transmittance at a wavelength of 365 nm such as i-line) is low, and the curing reaction in the deep part of the film after irradiation tends to be insufficient. Specifically, in particular, a solid-state imaging device having an optical density (OD) of 3.5 or more (preferably 4.0 or more) at a wavelength of 365 nm when a film having a thickness of 1.0 μm is used. This is effective in the case of a black photosensitive resin composition.

  Here, the “dissolution rate of the non-irradiated region” means pH (23 ° C.) 8 to 0.1% containing tetramethylammonium hydroxide and a nonionic surfactant with respect to the total mass of the developer. 12 is a speed in the thickness direction of a film when a film formed by applying a black photosensitive resin composition for a solid-state imaging device or the like using 12 developer (23 ° C.) is developed.

  The developer may be a developer having a pH (23 ° C.) of 8 to 12 containing 0.1% by mass of tetramethylammonium hydroxide (total mass of developer) and a nonionic surfactant, The content of the alkaline agent other than tetramethylammonium oxide is preferably 0.01 to 3.0% by mass with respect to the amount of tetramethylammonium hydroxide. Here, the alkali agent is a compound showing alkalinity, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, hydroxylated. Tetraethylammonium, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene and the like are included.

  The nonionic surfactant in the developer is not particularly limited. For example, polyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene alkyl ether, fatty acid alkanolamide, alkylamine oxide Etc. can be applied singly or as a mixture. The developer preferably has a nonionic surfactant content of 0.01 to 5.0% by mass with respect to the total mass of the developer.

  In order to set the dissolution rate when developing an unexposed area under specific development conditions to 0.005 to 0.060 μm / sec, selection of the component configuration and component type of the black photosensitive resin composition for a solid-state imaging device Further, it is possible to adjust appropriately from the composition side of the composition, such as an increase in the color material content. Specifically, for example, a bifunctional or higher (meth) acrylate monomer may be selected as the photopolymerizable compound, or the content of the photopolymerizable compound may be reduced and adjusted to a predetermined ratio.

Next, the component which comprises the black photosensitive resin composition for solid-state image sensors is explained in full detail.
(Coloring material for black)
The black photosensitive resin composition for a solid-state imaging device of the present invention contains at least one black color material. By containing a black color material, a light-shielding film can be formed. In addition to black pigments and black dyes, the black color material in the present invention includes mixed color materials in which chromatic pigments other than black, dyes, and the like are combined.

The content of the black color material in the black photosensitive resin composition for a solid-state imaging device of the present invention is such that the optical density (OD) at a wavelength of 365 nm is 3.5 or more when a film having a thickness of 1.0 μm is used (preferably Is preferably 4.0 or more). Specifically, the content of the black color material is preferably 50% by mass or more and more preferably 60% by mass or more based on the total solid content of the black photosensitive resin composition for a solid-state imaging device. The upper limit of the content of the color material for black is 70% by mass from the viewpoint of maintaining the relative amount of the component contributing to the photolithography performance to some extent, allowing the photocuring to proceed more effectively, and improving the substrate adhesion and the film strength. Is desirable. When the content is within the above range, a high optical density can be obtained with a thin film.
A black color material may contain only 1 type, or may contain 2 or more types.

In addition, the black photosensitive resin composition for a solid-state imaging device of the present invention is a known colorant such as a pigment or a dye such as red, blue, green, yellow, cyan, magenta, violet, or orange, instead of a black color material. In addition to a black color material, in addition to a black color material, pigments such as red, blue, green, yellow, cyan, magenta, violet, orange, etc. A known colorant such as a dye may be further added.
When using a color material such as another pigment or dye together with the black color material, the content ratio of the color material used in combination is 2 to 50 parts by mass with respect to 100 parts by mass of the total color material used with the black color material. A range is preferable, More preferably, it is 2-30 mass parts, Most preferably, it is 2-10 mass parts.

  As the black color material, carbon black, titanium black, iron oxide, manganese oxide, graphite, and the like are preferable from the viewpoint of realizing a high optical density in a small amount, and among these, carbon black and titanium black are preferable.

The average particle diameter (average primary particle diameter) 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 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 commercially available products such as carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960 manufactured by Mitsubishi Chemical Corporation. # 950, # 900, # 850, 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, Diamond Black 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 is dispersed in propylene glycol monomethyl ether so that benzyl methacrylate and methacrylic acid are in 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.

  In addition, the titanium black is a composite oxide such as Cu, Fe, Mn, V, and Ni, and a black pigment such as cobalt oxide, iron oxide, carbon black, and aniline black for the purpose of adjusting dispersibility, colorability, and the like. One or a combination of two or more types may be included. In this case, titanium black particles occupy 50% by mass or more of the pigment. 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. .

  Titanium black is produced by heating a mixture of titanium dioxide and metal titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (JP 57-205322 A), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (JP 60-65069 A, JP Sho 61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), etc. is not.

  As the titanium black, a commercially available product may be used. Examples of commercially available products include Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N manufactured by Mitsubishi Materials, and Tilac D manufactured by Ako Kasei.

  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. Therefore, the value measured by the BET method is usually 5 to 150 m. ^{About 2} / g, especially about 20 to 100 m ² / g is preferable.

  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, polymers obtained by polymerizing monomers such as (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamides or derivatives thereof, styrene or derivatives thereof are used as dispersants. be able to.
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, more preferably 800 to 50000. More preferably, it is 1000-30000.

  As a dispersion medium for dispersing a 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 dispersion solvent. 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 mono Glycols such as ethyl ether, polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether or derivatives thereof; glycerol or derivatives thereof such as glycerol, glycerol monoethyl ether, glycerol monoallyl ether; ethers such as tetrahydrofuran, dioxane; methyl ethyl ketone , Methyl isobu Ketones such as ruketone; liquid paraffin, decane, decene, methylnaphthalene, decalin, kerosene, diphenylmethane, toluene, dimethylbenzene, ethylbenzene, diethylbenzene, propylbenzene, cyclohexane, partially hydrogenated hydrocarbons such as triphenyl, poly Dimethylsiloxane, partially octyl-substituted polydimethylsiloxane, partially phenyl-substituted polydimethylsiloxane, silicone oils such as fluorosilicone oil, halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, bromobenzene, chlorodiphenyl, chlorodiphenylmethane, and dillol (Daikin) Kogyo Co., Ltd.), demnum (Daikin Kogyo Co., Ltd.) and other fluorides, ethyl benzoate, octyl benzoate, dioctyl phthalate, trimelli Ester compounds such as trioctyl acid, dibutyl sebacate, ethyl (meth) acrylate, butyl (meth) acrylate, dodecyl (meth) acrylate, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethyl Amide solvents such as acrylamide, N, N-dimethylacetamide, and N-methylpyrrolidone are appropriately selected and used alone or in combination.

(Photopolymerizable compound)
The black photosensitive resin composition for a solid-state imaging device of the present invention contains at least one photopolymerizable compound. By containing the photopolymerizable compound, it is possible to impart a polymerization curing function capable of patterning with light.

  As the photopolymerizable compound, an addition-polymerizable compound having at least one ethylenically unsaturated double bond can be used. Specifically, at least one, preferably two, terminal ethylenically unsaturated bonds are used. It can select from the compound group which has it above. Such a compound group has what is widely known in the said industrial field | area, for example, a monomer, a prepolymer, ie, a dimer, a trimer, an oligomer, those mixtures, those copolymers, etc. There are some chemical forms.

  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. Examples thereof include esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids, and amides of aliphatic polyvalent amine compounds and unsaturated carboxylic acids. 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 carboxylic acid is also preferably used. In addition, an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group and an addition reaction product of a monofunctional or polyfunctional alcohol, amine, or thiol, a halogen group, 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 the “ester of aliphatic polyhydric alcohol compound and unsaturated carboxylic acid” include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, Tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexane Diol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol tria Relate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanur Examples include acid EO-modified triacrylate.

  Further, as methacrylic acid esters, 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-hydroxy Propoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and the like.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaco And crotonic acid esters such as ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate, and isocrotonic acid esters. Examples include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetra malate, and the like.
Further, other examples of esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59. Those having an aromatic skeleton as described in JP-A-5241, JP-A-2-226149 and those containing an amino group as described in JP-A-1-165613 are also suitable. Furthermore, the ester monomer may be used as a mixture.

  Specific examples of the monomer of the “amide of aliphatic polyvalent amine compound and unsaturated carboxylic acid” 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 No. 54-21726.

Also suitable are urethane-based addition-polymerizable compounds produced by the addition reaction of isocyanate and hydroxyl groups. Specific examples thereof include two or more per molecule described in JP-B-48-41708. And a vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer having a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having an isocyanate group.
CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH (A)
[In General Formula (A), R ⁴ and R ⁵ each independently represent a hydrogen atom or CH ₃ . ]

  Also, urethane acrylates described in JP-A-51-37193, JP-B-2-32293, 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. Furthermore, in 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, the photosensitivity speed is high. A black photosensitive resin composition for a solid-state imaging device having a high speed can be obtained.

  Other examples include polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid. And polyfunctional acrylates and methacrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid-based compounds described in JP-A-2-25493. Etc. can also be mentioned. Further, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferable. 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.

  In the black photosensitive resin composition for a solid-state imaging device of the present invention, as a photopolymerizable compound, from the viewpoint of controlling the dissolution rate of the non-irradiated region at the time of development from 0.005 μm / sec to 0.060 μm / sec. Is preferably a bifunctional or higher functional (meth) acrylate monomer. Examples of the bifunctional or higher-functional (meth) acrylate monomer include, for example, the above-mentioned acrylic acid ester, methacrylic acid ester, and others (meth) in the above “ester of aliphatic polyhydric alcohol compound and unsaturated carboxylic acid”. Acrylic ester compounds can be preferably used.

In addition, the structure of the photopolymerizable compound constituting the photosensitive resin composition of the present invention, or the details of the usage method such as single use or combined use, addition amount, etc. are matched to the final performance design of the photosensitive resin composition. Can be set arbitrarily. 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 bifunctional or more is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). It is also effective to adjust both sensitivity and intensity by using both of these.
Photopolymerization is also possible with respect to compatibility and dispersibility with other components contained in the photosensitive resin composition (for example, photopolymerization initiators, black colorants (pigments, dyes), binder polymers, etc.). The selection and use method of the compatible compound is important. For example, the compatibility may be improved by using a low-purity compound or using two or more types in combination. In addition, a specific structure may be selected for the purpose of improving adhesion to a hard surface such as a support.

As content in the black photosensitive resin composition for solid-state image sensors of a photopolymerizable compound, the range of 5-20 mass% is preferable with respect to the total solid of a composition. In particular, a composition in which the content of the bifunctional or higher (meth) acrylate monomer with respect to the total solid content of the composition is 5 to 20% by mass is preferable.
When the content of the photopolymerizable compound is 5% by mass or more, good pattern formability and film strength are obtained while maintaining photocurability, and when the content is 20% by mass or less, the specific developer (23 ° C. ) Can be controlled to 0.005 to 0.060 μm / sec.
Among the above, for the same reason, the content of the photopolymerizable compound is more preferably 5 to 15% by mass, and particularly preferably 7.5 to 12.5% by mass.

(Photopolymerization initiator)
The black photosensitive resin composition for a solid-state imaging device of the present invention contains at least one photopolymerization initiator. It acts on the photopolymerizable compound and can be patterned by receiving light irradiation.

  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 properties, initiation efficiency, absorption wavelength, availability, cost, and the like. Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyloxadiazole 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-p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, -[M-Fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (Ethoxycarbonylmethyl) aminophenyl] -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 (Romethyl) -s-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-p -N-ethoxycarbonylmethylaminophenyl) -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-ethoxy) Carbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylamino) Nyl) -2,6-di (trichloromethyl) -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-p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-p -N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloro Methyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, and the like.

  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 and 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-methylmer) Captophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether, and the like are also usefully used.

Among these photopolymerization initiator species, an oxime photopolymerization initiator is preferable in that a pattern with a good rectangular profile can be obtained with a smaller exposure amount. The oxime photopolymerization initiator can be appropriately selected from known initiators such as oxime initiators described in JP 2000-80068 A, JP 2001-233842 A, and the like.
Specific examples of oxime photopolymerization initiators include commercially available compounds such as 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone (all manufactured by Ciba Specialty Chemicals). Among these, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is preferable for the same reason as described above.

  In addition to the above, a compound represented by the following general formula (1) can also be mentioned as a suitable polymerization initiator from the viewpoint that a pattern with a good rectangular profile can be obtained with a smaller exposure amount.

  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 oxime compound represented by the general formula (1) 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 oxime compound represented by the general formula (1) 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.

  Specific examples of the oxime compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.

  The oxime compound represented by the general formula (1) has a maximum absorption wavelength in a 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 455 nm are preferable. Thus, the oxime compound represented by the general formula (1) has absorption in a long wavelength region as compared with other conventional oxime compounds. Therefore, it exhibits excellent sensitivity when exposed to a light source of 365 nm or 405 nm.

In the oxime compound represented by the general formula (1), 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 the viewpoint of sensitivity. 200000 is particularly preferred.
Here, the molar extinction coefficient of the oxime compound represented by the general formula (1) is 0.01 g / L using an ultraviolet-visible spectrophotometer (Varry, Carry-5 spectrophotometer) using an ethyl acetate solvent. Measured at a concentration of

  The oxime compound represented by the general formula (1) in the present invention can be synthesized by, for example, the following method, but is not limited to this method.

  The oxime compound represented by the general formula (1) has a function as a photopolymerization initiator that decomposes by light and initiates and accelerates the polymerization of the photopolymerizable compound. The represented oxime compound has excellent sensitivity to a light source of 365 nm or 405 nm.

As content in the black photosensitive resin composition for solid-state image sensors of a photoinitiator, 0.1-20 mass% is preferable with respect to the total solid of a composition, and 3.0-15.0 mass % Is preferred. When the content of the photopolymerization initiator is 0.1% by mass or more, high exposure sensitivity is obtained, and when it is 20% by mass or less, it is advantageous in terms of pattern resolution.
A photoinitiator may be used individually by 1 type and may use 2 or more types together.

(solvent)
The black photosensitive resin composition for a solid-state imaging device 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)
The black photosensitive resin composition for a solid-state imaging device of the present invention can be constituted by using other components such as a binder, a sensitizer, a co-sensitizer, and a thermal polymerization inhibitor in addition to the above components. .

-Binder-
The photosensitive resin composition of the present invention may contain a resin as a binder. It is preferable to use a linear organic polymer as the resin. As a linear organic polymer, a well-known thing can be used arbitrarily. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer can be selected 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.

-Sensitizer-
The photosensitive resin composition of the present invention may contain a sensitizer. The sensitizer is preferably one that sensitizes the photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism.
Examples of the sensitizer include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 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), square Ums (eg, squalium), acridine orange, coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzene , 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. And 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. 0.1-20 mass% is preferable with respect to a composition total solid, and 0.5-15 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 co-sensitizers include amines such as MRSander et al., "Journal of Polymer Society", Vol. 10, page 3173 (1972), Japanese Examined Patent Publication No. 44-20189, Japanese Patent Laid-Open No. 51-82102. No. 5, No. 52-134692, No. 59-138205, No. 60-84305, No. 62-18537, No. 64-33104, Research Disclosure. Examples include compounds described in No. 33825, and 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, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, and JP-A-56. And the like. Specific examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene. Etc. Still other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and Japanese Patent Publication No. 55-34414. And hydrogen compounds described in JP-A-6-308727, etc. (eg, trithiane) 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-
The photosensitive resin composition of the present invention may contain a small amount of a thermal polymerization inhibitor. The thermal polymerization inhibitor can prevent unnecessary thermal polymerization of the photopolymerizable compound during production or storage of the composition. As thermal polymerization inhibitors, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol) 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
When the photosensitive resin composition of the present invention contains a thermal polymerization inhibitor, the content of the thermal polymerization inhibitor is about 0.01 to about 5% by mass with respect to the total solid content of the photosensitive resin composition. preferable.
Also, if necessary, from the viewpoint of preventing polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added, and it is unevenly distributed on the surface of the coating film during the drying process after coating. Also good. 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-
The photosensitive resin composition of the present invention may contain an adhesion improver and can improve the adhesion with a hard surface such as a support. 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 content of the adhesion improver is preferably 0.5 to 30% by mass with respect to the total solid content of the photosensitive resin composition. 7-20 mass% is more preferable.

-Other additives-
The photosensitive resin composition of the present invention may contain known additives such as inorganic fillers, plasticizers, and sensitizers. With these additives, the physical properties of the cured film can be improved. Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, and the like. When using resin, it can add in 10 mass% or less with respect to the total mass of a photopolymerizable compound and resin.

  The photosensitive resin composition for a solid-state imaging device of the present invention can be prepared by mixing and dispersing the above components using various mixers and dispersers.

The photosensitive resin composition for a solid-state image sensor of the present invention is suitable for use in forming a light-shielding film used for a solid-state image sensor such as a CCD or CMOS. That is, the present invention is particularly suitable for forming a color filter for a solid-state imaging device in which a colored pattern is formed in a thin film with a very small size and a good rectangular cross-sectional profile is required.
Specifically, in the case of a thin film having a thickness of 1 μm or less, the amount of components contributing to photolithographic properties excluding the colorant in the film is relatively reduced, and the amount of other components is further reduced by increasing the amount of the black colorant. As a result, the amount of transmission of light into the film decreases, and the lower film portion where the exposure amount is low is easily over-developed and becomes reversely tapered or the pattern is easily peeled off. This becomes conspicuous when the thickness of the film to be formed is 0.005 μm to 0.9 μm (further 0.1 μm to 0.7 μm). In addition, one size of the pattern formed with the photosensitive resin composition of the present invention (a size with a pattern viewed from the normal direction of the substrate) such as forming a light shielding film corresponding to the pixel pattern constituting the color filter is 2 μm. In the case of the following (for example, 0.5 to 2.0 μm), the pattern formability is easily impaired due to an increase in the amount of the black color material. This is particularly noticeable when the pattern size is 1.0 to 1.7 μm (further 1.2 to 1.5 μm).
In the case of forming such a color filter for a solid-state imaging device, the pattern forming property is effectively improved by using the photosensitive resin composition of the present invention, and a pattern close to a rectangle is obtained. In addition to high sensitivity, the adhesion of the formed pattern to the substrate and the like is also improved, and the occurrence of peeling and hence the occurrence of image defects is prevented.

<Image forming method>
The image forming method of the present invention irradiates a film formed of a black photosensitive resin composition containing at least a black colorant, a photopolymerizable compound, and a photopolymerization initiator (hereinafter referred to as “light irradiation process”). After that, the light-irradiated region of the formed film is dissolved at a dissolution rate of 0.005 μm / sec or more and 0.060 μm / sec or less using a developer (hereinafter also referred to as “development process”). )) To form a black pattern for a solid-state imaging device.

  The black photosensitive resin composition of the present invention described above is suitable as the black photosensitive resin composition, and details and preferred embodiments of the black colorant, the photopolymerizable compound, and the photopolymerization initiator are described above. It is as follows.

  In the image forming method of the present invention, the development in the non-light-irradiated region is performed by adjusting the dissolution rate when the light-unirradiated region of the formed film is developed to 0.005 to 0.060 μm / sec. In the exposed area in the vicinity of the unirradiated light-irradiated area where the speed is suppressed and dissolved in the developer relatively quickly, the deep part of the film where the progress of the curing reaction is insufficient, that is, the dissolution of the pattern lower film part close to the substrate, That is, since it becomes possible to suppress over-development, while maintaining the developability itself and preventing the occurrence of development residues, reverse tapering of the pattern is avoided, and a rectangular pattern with a good cross-sectional profile is obtained. The substrate adhesion of the pattern is also improved.

The film, which is an object to be irradiated with light, is coated with a black photosensitive resin composition containing at least a black colorant, a photopolymerizable compound, and a photopolymerization initiator on a desired substrate, or discharged by an inkjet method. Can be formed (film forming step).
As a coating method in the case of coating, various coating methods such as slit coating, spin coating, cast coating, roll coating, and screen printing can be applied. Moreover, after application | coating, generally the coating film of the photosensitive resin composition is dried on 70 to 110 degreeC on the conditions for 2 to 4 minutes.
The film thickness of the film formed by coating or the like is preferably 0.35 μm to 1.5 μm, more preferably 0.40 μm to 1.0 μm, from the viewpoint of resolution and developability.

  Examples of the substrate include a photoelectric conversion device substrate used for a solid-state imaging device or the like, such as a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like. If necessary, an undercoat layer may be provided on the substrate to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the substrate surface.

-Light irradiation process-
In the light irradiation step, the film formed of the black photosensitive resin composition is irradiated with light, and a light irradiated region and a light non-irradiated region are formed on the film to form a latent image that forms a pattern after development.
Irradiation in the light irradiation step can be performed, for example, by using a desired light source and applying light to the film in a pattern through a mask. In this case, only the part of the coating film irradiated with light can be cured.

Irradiation is preferably performed by irradiation of radiation, and as radiation, ultraviolet rays such as g-line and i-line are preferable, and a high-pressure mercury lamp is more preferable. Irradiation intensity ^is more preferably 5mJ / ^{m 2} ~1500mJ / m 2 is preferably ^{10mJ / m 2 ~1000mJ / m 2} , 10mJ / m 2 ~800mJ / m 2 is most preferred.

The exposure may be performed by any of the proximity method, the mirror projection method, and the stepper method, but the exposure is particularly preferably performed by the stepper method (reduced projection exposure method using a reduced projection exposure machine). . In the stepper method, a pattern is formed by performing exposure while varying the exposure amount stepwise, and the rectangularity of the pattern can be particularly improved when performing stepper exposure.
Moreover, as an exposure apparatus used for stepper exposure, for example, an i-line stepper (trade name: FPA-3000i5 +, manufactured by Canon Inc.) can be used.

-Development process-
In the development step, the light-irradiated region of the film formed in the light irradiation step is dissolved at a dissolution rate of 0.005 μm / sec or more and 0.060 μm / sec or less using a developer, and a black pattern for a solid-state imaging device Form. In this step, the latent image formed in the light irradiation step is exposed, leaving only the cured portion, and a light-shielding pattern is formed.

When the dissolution rate of the light unexposed area is less than 0.005 μm / sec, not only a long time is required for development, but also a development residue is likely to occur, and when it exceeds 0.060 μm / sec, Overdevelopment occurs in the deep part of the film, specifically in the lower film part close to the substrate of the film, and the cross-sectional profile of the formed pattern becomes a reverse taper shape, and a good rectangular pattern cannot be obtained after development. In addition, the adhesion with the substrate is also reduced.
In particular, when the black density is high, the light transmittance upon irradiation (for example, the light transmittance at a wavelength of 365 nm such as i-line) is low, and the curing reaction in the deep part of the film after irradiation tends to be insufficient. Specifically, in particular, a solid-state imaging device having an optical density (OD) of 3.5 or more (preferably 4.0 or more) at a wavelength of 365 nm when a film having a thickness of 1.0 μm is used. This is effective when a film is formed with the black photosensitive resin composition for use.

  The “dissolution rate of the non-irradiated region” referred to in the image forming method of the present invention is a rate in the film thickness direction during development of a film formed by applying a photosensitive resin composition or the like.

As the developer in the image forming method of the present invention, an alkaline aqueous solution obtained by diluting an organic alkaline compound 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. it can. Examples of the organic alkaline compound include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0]- 7-Undecene etc. are included.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

In the present invention, dissolution of the non-irradiated region when developed at 23 ° C. using a developer having a pH (23 ° C.) of 8 to 12 containing 0.1% by mass of tetramethylammonium hydroxide and a nonionic surfactant. An embodiment in which development is performed so that the speed is in the range of 0.005 to 0.060 μm / sec is preferable. In this case, in particular, a reverse rectangular taper of the cross-sectional profile of the pattern is prevented, and a good rectangular black pattern is obtained, and the adhesion to the substrate is also improved.
In this case, the content of the alkali agent other than tetramethylammonium hydroxide is preferably 0.01 to 3.0% by mass with respect to the amount of tetramethylammonium hydroxide. Here, the alkaline agent is a compound that exhibits alkalinity in an aqueous solution, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine. , Tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene and the like.

  In addition, when using the developing solution which is alkaline aqueous solution, the process wash | cleaned (rinsing) with a pure water is generally provided after image development.

  In addition, after performing said film formation process, light irradiation process, and image development process, you may include the hardening process which hardens | cures the formed pattern by heating and / or exposure as needed.

  In the above-described black photosensitive resin composition and image forming method for a solid-state imaging device according to the present invention, the black photosensitive resin composition having excellent adhesion, rectangularity, line width, and other shapes (for example, a color filter having the black pattern). A solid-state imaging device having excellent color reproducibility.

The configuration of the solid-state imaging device is not particularly limited as long as the configuration includes a color filter and functions as a solid-state imaging device, and examples thereof include the following configurations.
A support body has a plurality of photodiodes constituting a light receiving area of a CCD image sensor (solid-state imaging device) and a transfer electrode made of polysilicon or the like, and only the light receiving portion of the photodiode is placed on the photodiode and the transfer electrode. A light-shielding film made of tungsten or the like having an opening; a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion; and a color on the device protective film A configuration having a filter.
Further, a configuration having light collecting means (for example, a microlens, etc., the same applies hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light collecting means on the color filter Etc.

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

Example 1
<Fabrication of wafer with flattening film>
(1) Preparation of planarization film resist solution The components of the following composition were mixed and stirred with a stirrer to prepare a planarization film resist solution.
<Composition of resist solution for flattening film>
Benzyl methacrylate / methacrylic acid copolymer: 16.4 parts (= 70/30 [molar ratio], weight average molecular weight: 30000, manufactured by Fujikura Kasei Co., Ltd., product name: Acrybase FF-187)
・ Dipentaerythritol pentaacrylate: 6.5 parts (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
Propylene glycol monomethyl ethyl acetate 13.8 parts (Daicel Chemical Industries, product name: MMPMAC)
Ethyl-3-ethoxypropionate 12.3 parts (manufactured by Nagase Sangyo Co., Ltd., product name: ethyl-3 ethoxypropionate)
・ The following triazine-based initiator: 0.3 part (manufactured by PANCHIM, product name: triazine PP)

(2) Formation of flattened film A 6-inch silicon wafer is prepared, and the flattened film resist solution obtained above is uniformly applied to the wafer by spin coating to form a coated film, and the formed coating is formed. The film was heat-treated on a hot plate having a surface temperature of 120 ° C. for 120 seconds. Here, the spin coating was performed by adjusting the coating rotation speed so that the thickness of the coating film after the heat treatment was about 1 μm. Next, the heat-treated coating film was further heat-treated in an oven at 220 ° C. for 1 hour, and the coating film was cured to obtain a flattened film.
As described above, a wafer with a planarization film in which a planarization film was formed on a 6-inch silicon wafer was obtained.

<Preparation of black photosensitive resin composition>
Components of the following composition were mixed to prepare a black photosensitive resin composition.
<Composition>
Pigment dispersion A (K-02884-2, manufactured by Toyo Ink Manufacturing Co., Ltd.) ... 64.4 parts [Black pigment (carbon black) 19.4% by mass (solid content of black pigment = 23% by mass)] 8.9% by weight of dispersant, 16.1% by weight of cyclohexanone, and 55.6% by weight of propylene glycol monomethyl ether acetate)
Resin A: 7.18 parts [45% solution of benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer in propylene glycol monomethyl ether acetate, weight average molecular weight: 30000, Fujikura Kasei ( Product name: Acrybase FF-187]
Photopolymerizable monomer A (dipentaerythritol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd., product name: KAYARAD DPHA) ... 1.82 parts Photoinitiator A (the following oxime compound I, Ciba Specialty Chemicals) Product name: IRGACURE OXE02) ... 1.71 parts / solvent (propylene glycol monomethyl ether acetate, manufactured by Daicel Chemical Industries, Ltd., product name: MMPGC) ... 25.4 parts / surface activity Agent A: 0.42 part (Megafac F-144, manufactured by Dainippon Ink & Chemicals, Inc .; fluorinated surfactant)
・ Polymerization inhibitor A (manufactured by Kanto Chemical Co., Ltd., product name: p-methoxyphenol): 0.001 part

* Oxime compounds I

<Preparation of black film>
The black photosensitive resin composition obtained above was applied by spin coating on the flattened film of the silicon wafer, and then dried by heat treatment on a hot plate at a temperature of 120 ° C. for 120 seconds, A black film having a dry film thickness of 1.0 μm was formed.

<Formation of black pattern>
Next, an i-line stepper (Canon Co., Ltd.) is passed through a mask pattern in which a square pixel pattern of 5.0 μm square is arranged in a matrix shape in a 4 mm × 3 mm region on the black film after drying. FPA-3000i5 +) manufactured by the company was exposed at an exposure amount of 100 to 3000 mJ / m ² . After pattern exposure, the black film is a 60% aqueous solution of organic alkaline developer CD-2000 (Fuji Film Electronics Materials Co., Ltd.) [tetramethylammonium hydroxide is 0.3% by mass and nonionic interface Paddle development was performed at 23 ° C. for 60 seconds using an aqueous solution containing an activator (pH = 10).
Then, it rinsed with the pure water for 20 seconds with the spin shower. After further washing with pure water, water droplets were blown off with high-pressure air, the silicon wafer was naturally dried, and post-baked on a hot plate at 220 ° C. for 300 seconds.
As described above, a black pattern was formed on the silicon wafer.

<Evaluation>
The following evaluation was performed about the black photosensitive resin composition and black pattern which were obtained above. The results of evaluation and measurement are shown in Table 2 below.

-1. Sensitivity
The minimum amount of light irradiation in which the thickness of the light irradiation region did not change due to the development treatment was determined and used as an index for evaluating sensitivity. The sensitivity indicates that the smaller the value of the light irradiation amount, the higher the sensitivity.

-2. Dissolution rate of black film
A black film formed on a silicon wafer was replaced with a 60% aqueous solution of an organic alkaline developer CD-2000 (an aqueous solution containing 0.1% by mass of tetramethylammonium hydroxide and a nonionic surfactant, 23 C., pH = 10], the immersion time was counted from 0 to 120 seconds in increments of 10 seconds, and the time until the black film completely disappeared was defined as the elution time. The dissolution rate [μm / sec] per unit second was calculated from the obtained elution time and the thickness of the black film.

-3. Optical density
The optical density at a wavelength of 365 nm of the black film before exposure and development formed on the flattened film of the silicon wafer was measured with a Macbeth densitometer (TD-904, manufactured by Macbeth), and the film thickness was 1.0 μm. The optical density (OD ³⁶⁵ ) at a certain time was determined.

-4. Substrate adhesion
Of the pixel patterns formed in a matrix, the presence or absence of pattern defects due to peeling from the silicon wafer was observed with a length measurement SEM (S-7800H, manufactured by Hitachi, Ltd.) and evaluated according to the following evaluation criteria. did.
<Evaluation criteria>
○: No pattern defect was observed.
(Triangle | delta): Although the pattern defect | defect was hardly observed, the defect | deletion was partially observed.
X: Remarkably many pattern defects were observed.

-5. Development residue
In the pattern formation surface of the silicon wafer after the development treatment, the presence or absence of a residue in a region not irradiated with light (unirradiated region) was observed with a length measurement SEM (S-7800H, manufactured by Hitachi, Ltd.), and the following Evaluation was performed according to the evaluation criteria.
<Evaluation criteria>
○: No residue was observed in the unirradiated area.
Δ: A slight residue was confirmed in the non-irradiated area, but it was not problematic in practical use.
X: Residue was remarkably confirmed in the unirradiated area.

-6. Pattern shape
SEM (S-4800, Hitachi High-Technologies Corporation) shows the pattern shape of the post-baked pixel pattern formed on the silicon wafer when cut by a plane parallel to the normal direction of the wafer surface. The rectangularity of the cross-sectional profile was evaluated. The cross-sectional profile of the pattern is most preferably rectangular and may be slightly forward tapered, but a reverse tapered shape is not preferable.

(Examples 2 to 5)
In Example 1, except that the composition of the black photosensitive resin composition was changed as shown in Table 1 below, a black photosensitive resin composition was prepared and a black pattern was formed in the same manner as in Example 1. In addition, the same evaluation was performed. The results of evaluation and measurement are shown in Table 2 below.

(Comparative Examples 1-4)
In Example 1, except that the composition of the black photosensitive resin composition was changed as shown in Table 1 below, a black photosensitive resin composition was prepared and a black pattern was formed in the same manner as in Example 1. In addition, the same evaluation was performed. The results of evaluation and measurement are shown in Table 2 below.

Hereinafter, the structures of the compounds described in the column of the photopolymerizable compound in Table 1 are shown.

As shown in Table 2 above, in the examples, even when the film has an OD ^{365 at 365} nm of 3.5 or more, pattern formation with high sensitivity is achieved when the dissolution rate in development is in the range of 0.005 to 0.060 um / s. It was also possible in terms of adhesion to the wafer, development residue, and pattern shape.
On the other hand, in the comparative example in which the dissolution rate exceeds 0.060 um / s, pattern formation cannot be performed. Conversely, in the case of less than 0.005 um / s (comparative example 4), the color remains.

Claims (9)

At least a black colorant, a photopolymerizable compound, and a photopolymerization initiator,
The dissolution rate of the non-irradiated region is 0.005 μm when developed at 23 ° C. using a developer having a pH (23 ° C.) of 8 to 12 containing 0.1% by mass of tetramethylammonium hydroxide and a nonionic surfactant. The black photosensitive resin composition for solid-state image sensors which is / sec or more and 0.060 micrometer / sec or less.   2. The black photosensitive resin composition for a solid-state imaging device according to claim 1, wherein an optical density (OD) at a wavelength of 365 nm when the film is 1.0 μm thick is 3.5 or more.   The black photosensitive resin composition for a solid-state imaging device according to claim 1, wherein the black color material is at least one of carbon black and titanium black.   4. The black photosensitive resin composition for a solid-state imaging device according to claim 1, wherein the photopolymerization initiator is an oxime-based initiator.   At least one of the photopolymerizable compounds is a bifunctional or higher (meth) acrylate monomer, and the content of the photopolymerizable compound is 5 to 20% by mass with respect to the total solid content of the composition. The black photosensitive resin composition for a solid-state imaging device according to any one of claims 1 to 4, characterized in that the black photosensitive resin composition is used.   After irradiating light to a film formed of a black photosensitive resin composition containing at least a black colorant, a photopolymerizable compound, and a photopolymerization initiator, a light unirradiated region of the film is formed using a developer. An image forming method for forming a black pattern for a solid-state imaging device by dissolving at a dissolution rate of 0.005 μm / sec or more and 0.060 μm / sec or less.   The image forming method according to claim 6, wherein the developer contains 0.1% by mass of tetramethylammonium hydroxide and a nonionic surfactant, and has a pH (23 ° C.) of 8-12.   The image forming method according to claim 6, wherein the optical density (OD) of the film at a wavelength of 365 nm is 3.5 or more.   At least one of the photopolymerizable compounds is a bifunctional or higher (meth) acrylate monomer, and the content of the photopolymerizable compound in the black photosensitive resin composition is the total solid of the black photosensitive resin composition. The image forming method according to claim 6, wherein the content is 5 to 20% by mass with respect to the minute.