JP5235546B2 - Photosensitive resin composition, light-shielding color filter, method for producing the same, and solid-state imaging device - Google Patents

Description

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

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

On the other hand, coloring including a copolymer containing a structural unit derived from an N-substituted maleimide as a colored radiation-sensitive composition that is capable of forming a pixel and a black matrix having high sensitivity and excellent solvent resistance and adhesion. Radiation sensitive compositions are known (see, for example, Patent Document 6).
Japanese Patent Laid-Open No. 10-246955 JP-A-9-54431 Japanese Patent Laid-Open No. 10-46042 JP 2006-36750 A JP 2007-115921 A JP 2007-264377 A

Conventionally, a light-shielding photosensitive resin composition for a solid-state imaging device has been used for applications in which a pattern is formed on a flat portion for the purpose of shielding light around an image sensor and preventing reflection between pixels.
However, in recent years, the structure of the object to be coated has become complicated with downsizing of the solid-state imaging device, and it has been required to form a pattern with good film thickness uniformity on a substrate having a step. Under such circumstances, the above-described conventional composition may reduce film thickness uniformity when a pattern is formed on a stepped substrate, and improvement is required.

This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, the present invention provides a photosensitive resin composition capable of forming a pattern having excellent film thickness uniformity on a stepped substrate, a light-shielding color filter having excellent light-shielding ability uniformity, and a method for producing the same. It is an object of the present invention to provide a solid-state imaging device with little noise and excellent color reproducibility.

In the system using titanium black as the black pigment of the photosensitive resin composition, the present inventor uses a resin containing a structural unit derived from N-substituted maleimide as the resin component, so that the film thickness of the pattern formed is uniform. Based on this finding, the present invention has been completed.
That is, specific means for solving the above-described problems are as follows.
<1> Titanium black, a photopolymerizable compound, a resin containing a structural unit derived from N-substituted maleimide, a photopolymerization initiator, and a solvent , wherein the resin is (a) N-substituted maleimide (B) at least one selected from the group consisting of an unsaturated carboxylic acid, an acid anhydride of an unsaturated carboxylic acid, and an unsaturated phenol compound, (c) an unsaturated compound having a tetrahydrofuran skeleton, and (d) ) A photosensitive resin composition comprising a copolymer of (a), (b) and an unsaturated compound other than (c) .
<2> Titanium black, a photopolymerizable compound, a resin containing a structural unit derived from N-substituted maleimide, a photopolymerization initiator, and a solvent, wherein the titanium black has a particle size of 10 to 500 nm. It is a certain photosensitive resin composition.
<3> The specific surface area of the titanium black is the photosensitive resin composition according to <1> or <2>, in which a value measured by a BET method is 20 to 100 m ² / g.
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the titanium black content in the photosensitive resin composition is 15 to 95% by mass.

< 5 > The photosensitive resin composition according to any one of <1> to < 4 > , wherein the photopolymerization initiator is an oxime photopolymerization initiator.
< 6 > A light-shielding color filter formed using the photosensitive resin composition according to any one of <1> to < 5 >.

<7> A light-shielding color filter having a step of forming a pattern by applying the photosensitive resin composition according to any one of <1> to < 5 > onto a support, exposing through a mask, and developing the photosensitive resin composition. It is a manufacturing method.
<8> A solid-state imaging device including the light-shielding color filter according to < 6 >.

  According to the present invention, a photosensitive resin composition capable of forming a pattern having excellent film thickness uniformity on a stepped substrate, a light-shielding color filter having excellent light-shielding ability uniformity, and a method for producing the same. In addition, it is possible to provide a solid-state imaging device with little noise and excellent color reproducibility.

≪Photosensitive resin composition≫
The photosensitive resin composition of the present invention, titanium black, a photopolymerizable compound, a resin containing a structural unit derived from N- substituted maleimide, a photopolymerization initiator, and a solvent, only contains the resin (A) N-substituted maleimide; (b) at least one selected from the group consisting of unsaturated carboxylic acids, acid anhydrides of unsaturated carboxylic acids, and unsaturated phenol compounds; and (c) a tetrahydrofuran skeleton. and an unsaturated compound having, (d) said (a), wherein (b) and the and (c) other than the unsaturated compound, a is configured and that Do copolymer.
By setting the photosensitive resin composition to the configuration of the present invention, a pattern having excellent film thickness uniformity can be formed on a stepped substrate. Note that a pattern having excellent film thickness uniformity can be formed on a substrate having no step.
Hereinafter, each component of the photosensitive resin composition will be described.

<Titanium Black>
The photosensitive resin composition of the present invention contains titanium black.
The titanium black is black particles (black pigment) having titanium atoms. 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 JP-A-2007-302836. Processing is also possible.
Further, the titanium black is at least a composite oxide such as Cu, Fe, Mn, V, Ni, etc., or a black pigment such as cobalt oxide, iron oxide, carbon black, aniline black, etc. for the purpose of adjusting dispersibility, colorability and the like. It may be contained together with one kind, and in this case, it is preferable that 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. .

Examples of commercially available titanium black products include Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N manufactured by Mitsubishi Materials Corporation (Gemco Co., Ltd.), Tilac (Tilac) ) D and the like.
In this invention, titanium black may be used individually by 1 type, and may use 2 or more types together.

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

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

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

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

In addition, as other dispersants, a polymer obtained by polymerizing monomers such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide or a derivative thereof, styrene or a derivative thereof, or the above-described monomer may be used. A copolymer obtained by polymerization can be used as a dispersant.
Examples of the monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-phenylstyrene, o-chlorostyrene, m- Styrene monomers such as chlorostyrene and p-chlorostyrene; acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, stearyl acrylate, 2-acrylic acid 2- Ethylhexyl, hydroxyethyl acrylate, hydroxypropyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, methacrylate (Meth) acrylic 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.
In the present specification, (meth) acrylic acid represents acrylic acid or methacrylic acid, (meth) acryloyl represents acryloyl or methacryloyl, (meth) acrylate represents acrylate or methacrylate, and (meth) acrylamide represents acrylamide. Or represents methacrylamide.

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.
Further, from the viewpoint of further improving the film thickness uniformity (particularly the film thickness uniformity when a pattern is formed on a stepped substrate), the N-substituted maleimide described later is used as a resin used for dispersion of titanium black. It is preferable to use a resin containing a structural unit derived from.

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

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

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

In preparing the titanium black dispersion in the present invention, it is preferable to add 5 to 200 parts by mass, more preferably 10 to 100 parts by mass of the polymer component with respect to 100 parts by mass of titanium black.
When the polymer component is 5 parts by mass or more, the surface property of the titanium black can be kept better, and when the polymer component is 200 parts by mass or less, the originally required titanium black such as light-shielding property and coloring property can be maintained. The characteristics can be further improved.

The content of titanium black in the photosensitive resin composition is not particularly limited, but is preferably as high as possible in order to obtain a high optical density with a thin film, preferably 5 to 98% by mass, and 10 to 95. % By mass is more preferable, and 15 to 95% by mass is particularly preferable.
When the titanium black is 5% by mass or more, a higher optical density can be obtained even when the film thickness is thin, and when it is 98% by mass or less, the photocuring is promoted more effectively and the strength of the film is improved. The development latitude can be widened.

<Other black color materials, etc.>
In the photosensitive resin composition of the present invention, other black color materials may be used in combination with titanium black.
As the other black color material, various known black pigments and black dyes can be used, and carbon black, iron oxide, manganese oxide, graphite and the like are particularly preferable from the viewpoint of realizing a high optical density with a small amount. Of these, carbon black is preferred.

The average primary particle size (average primary particle size) of the other 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.

  In the present invention, when using other black color material in addition to titanium black, the total content of titanium black and other black color material in the photosensitive resin composition is not particularly limited, optical density, From the viewpoint of film strength, development latitude, etc., 5 to 98% by mass is preferable, 10 to 95% by mass is more preferable, and 15 to 95% by mass is particularly preferable.

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

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

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

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

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

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

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

The photosensitive resin composition of the present invention includes red, blue and green for the purpose of controlling the light-shielding property of a desired wavelength in addition to the aforementioned titanium black and other black color materials used as necessary. It is also possible to add known colorants such as pigments or dyes such as yellow, cyan, magenta, violet and orange.
The combined colorant (the combined colorant) is used in an amount of 2 to 50 parts by mass of the combined colorant with respect to 100 parts by mass of the total of the above-described titanium black and other black color materials used as necessary and the combined colorant Preferably, the combined colorant is 2 to 30 parts by mass, and most preferably the combined colorant is 2 to 10 parts by mass.

<Resin containing structural units derived from N-substituted maleimide>
The photosensitive resin composition of the present invention contains a resin containing a structural unit derived from N-substituted maleimide.
Here, the resin containing a structural unit derived from N-substituted maleimide refers to a resin prepared using N-substituted maleimide as a monomer. Among them, N- substituted maleimide and, copolymer including with other monomer (may be two or more types may be only one).
The resin containing a structural unit derived from N-substituted maleimide is preferably a resin that is soluble in an alkali developer (that is, an alkali-soluble resin).

Examples of the N-substituted maleimide in the present invention include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Nt-butylmaleimide, Examples thereof include Nn-hexylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-1-naphthylmaleimide and the like.
Among these, N-cyclohexylmaleimide, N-phenylmaleimide, and the like are preferable from the viewpoint of further improving film thickness uniformity (particularly, film thickness uniformity when a pattern is formed on a stepped substrate). N-phenylmaleimide is preferred.
The N-substituted maleimide may be used alone or in combination of two or more.

In the present invention, the resin containing a structural unit derived from an N-substituted maleimide is from the viewpoint of further improving the film thickness uniformity (particularly the film thickness uniformity when forming a pattern on a stepped substrate). (B) selected from the group consisting of an unsaturated carboxylic acid, an acid anhydride of an unsaturated carboxylic acid, and an unsaturated phenol compound. At least one (hereinafter also referred to as “component (b)”), (c) an unsaturated compound having a tetrahydrofuran skeleton (hereinafter also referred to as “component (c)”), and (d) the component (a). the (b) component and the (c) other than the component unsaturated compound (hereinafter, also referred to as "component (d)") and a copolymer (hereinafter, also referred to as "copolymer a") to including .

~ (A) component ~
Specific examples and preferred ranges of the component (a) in the copolymer A are as described above. In the copolymer A, the component (a) may be one type or two or more types.

~ (B) component ~
Among the components (b) in the copolymer A, examples of the unsaturated carboxylic acid or the acid anhydride of the unsaturated carboxylic acid include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic Unsaturated monocarboxylic acids such as acids; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like; Unsaturated polyvalent carboxylic acids or anhydrides thereof; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and other polyvalent carboxylic acids having two or more valences Mono [(meth) acryloyloxyalkyl] esters; ω-carboxypolycaprolactone mono (meth) acrylate, etc. And mono (meth) acrylates of polymers having a silyl group and a hydroxyl group.
Of the unsaturated carboxylic acids or acid anhydrides of the unsaturated carboxylic acids, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are light ester HOA-MS and light ester, respectively. Commercially available under the trade name HOA-MPE (manufactured by Kyoeisha Chemical Co., Ltd.).

  Examples of the unsaturated phenol compound include o-vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, and o-isopropenylphenol. , M-isopropenylphenol, p-isopropenylphenol and the like; 2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol , Unsaturated naphthols such as 2-isopropenyl-1-naphthol and 3-isopropenyl-1-naphthol;

In the copolymer A, as the component (b), (meth) acrylic acid, p-vinylphenol and the like are preferable, and (meth) acrylic acid is particularly preferable.
In the copolymer A, the component (b) may be one type or two or more types.

~ (C) component ~
Examples of the component (c) in the copolymer A include tetrahydrofuran esters of (meth) acrylic acid such as tetrahydrofuran-2-yl (meth) acrylate and tetrahydrofuran-3-yl (meth) acrylate; tetrahydrofurfuryl ( Tetrahydro of (meth) acrylic acid such as (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (tetrahydrofurfuryloxy) ethyl (meth) acrylate, 2- (3-tetrahydrofurfuryloxy) ethyl (meth) acrylate Furfuryl group-containing esters;

Phthalic acid [2- (meth) acryloyloxyethyl] (tetrahydrofuran-2-yl), phthalic acid [2- (meth) acryloyloxyethyl] (tetrahydrofuran-3-yl), succinic acid [2- (meth) acryloyloxy (Meth) acryloyl group-containing tetrahydrofuran esters of divalent carboxylic acids such as ethyl] (tetrahydrofuran-2-yl) and succinic acid [2- (meth) acryloyloxyethyl] (tetrahydrofuran-3-yl); phthalic acid [2 (Meth) acryloyl group-containing tetrahydrofurfuryl esters of divalent carboxylic acids such as-(meth) acryloyloxyethyl] (tetrahydrofurfuryl), succinic acid [2- (meth) acryloyloxyethyl] (tetrahydrofurfuryl);

Tetrahydrofuran esters of 2- (meth) acryloyloxypropionic acid such as tetrahydrofuran-2-yl 2- (meth) acryloyloxypropionate and tetrahydrofuran-3-yl 2- (meth) acryloyloxypropionate; 2- (meth) Tetrahydrofurfuryl acryloyloxypropionate, 2- (meth) acryloyloxypropionate 3-tetrahydrofurfuryl, 2- (meth) acryloyloxypropionate 2- (tetrahydrofurfuryloxy) ethyl, 2- (meth) acryloyloxypropion Tetrahydrofurfuryl group-containing esters of 2- (meth) acryloyloxypropionic acid, such as the acid 2- (3-tetrahydrofurfuryloxy) ethyl;

(Tetrahydrofuran-2-yl) oxy-p-vinylbenzene, tetrahydrofurfuryloxy-p-vinylbenzene, vinylbenzene derivatives such as 2- (tetrahydrofurfuryloxy) ethoxy-p-vinylbenzene; Yl) vinyl ether, (tetrahydrofurfuryl) vinyl ether, vinyl ethers such as [2- (tetrahydrofurfuryloxy) ethyl] vinyl ether, and the like.

In the present invention, the component (c) is preferably tetrahydrofurfuryl (meth) acrylate, succinic acid [2- (meth) acryloyloxyethyl] (tetrahydrofurfuryl), or the like.
In the present invention, the component (c) may be one type or two or more types.

~ (D) component ~
Examples of the component (d) include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxy. Aromatic vinyl compounds such as styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether; Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydi Unsaturated carboxylic acid esters such as propylene glycol (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and glycerol mono (meth) acrylate Kind;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethyl Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl (meth) acrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; Vinyl cyanide such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide Compound; unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide; vinyl carboxylate such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate Esters; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl (meth) acrylate, poly-n- And macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain such as butyl (meth) acrylate and polysiloxane.
In the present invention, the component (d) may be one type or two or more types.

Next, preferable combinations of the components (a) to (d) for producing the copolymer A will be described.
That is, (a) component is N-cyclohexylmaleimide and / or N-phenylmaleimide, (b) component is one or more unsaturated compounds containing (meth) acrylic acid, (c) The component is tetrahydrofurfuryl (meth) acrylate and / or succinic acid [2- (meth) acryloyloxyethyl] (tetrahydrofurfuryl), and the component (d) is styrene, methyl (meth) acrylate, n- Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer, and polymethyl methacrylate At least selected from the group of macromonomers The combination is one are preferred.

  Hereinafter, although the specific example of the copolymer A in this invention is illustrated, this invention is not limited to the following specific examples.

Examples of the copolymer A include:
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / methyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / methyl (meth) acrylate / n-butyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / methyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / methyl (meth) acrylate / n-butyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / methyl (meth) acrylate / n-butyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,

(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer Polymer,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer ,
(Meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polymethyl methacrylate macromonomer Polymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / allyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / tetrahydrofurfuryl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / allyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate / allyl (meth) acrylate Coalescence,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate / benzyl (meth) acrylate Coalescence,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate / allyl (meth) acrylate Coalescence,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate / benzyl (meth) acrylate Coalescence,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / n-butyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono ( (Meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-cyclohexylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meta ) Acrylate copolymer,
Is mentioned.

  Moreover, the copolymer etc. which replaced the tetrahydrofurfuryl (meth) acrylate in the copolymer enumerated above by the succinic acid [2- (meth) acryloyloxyethyl] (tetrahydrofurfuryl) can be mentioned.

  Among those exemplified above, the copolymer A in the present invention includes (meth) acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate copolymer, (meta ) Acrylic acid / N-phenylmaleimide / tetrahydrofurfuryl (meth) acrylate / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / N-phenylmaleimide / Succinic acid [2- (meth) acryloyloxyethyl] tetrahydrofurfuryl / styrene / n-butyl (meth) acrylate copolymer, (meth) acrylic acid / N-phenylmaleimide / succinic acid [2- (meth) acryloyloxy Ethyl] tetrahydrofurfuryl / styrene / - butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer is preferred.

  In the copolymer A, the copolymerization ratio of the component (a) is preferably 1 to 50% by mass, particularly preferably 5 to 40% by mass, and the copolymerization ratio of the component (b) is preferably 1 to 50% by mass. It is 40 mass%, Most preferably, it is 5-30 mass%, The copolymerization ratio of (c) component becomes like this. Preferably it is 1-70 mass%, Most preferably, it is 10-40 mass%. (D) The copolymerization ratio of a component becomes like this. Preferably it is 1-80 mass%, Most preferably, it is 5-60 mass%. By setting the copolymerization ratio within the above range, sensitivity, substrate adhesion, and solvent resistance can be further improved.

The photosensitive resin composition of the present invention may contain other resins (preferably alkali-soluble resins) in addition to the “resin containing a structural unit derived from N-substituted maleimide” described above.
The other resin is not particularly limited. For example, an alkali-soluble resin having a carboxyl group is preferable. Specifically, the unsaturated carboxylic acid and unsaturated carboxylic acid anhydride exemplified for the copolymer A are used. A copolymer of at least one selected from the group of the above and at least one selected from the group of the N-substituted maleimide and the component (d) is preferred.

  More specifically, as the other resin, (i) at least one unsaturated carboxylic acid having (meth) acrylic acid as an essential component, and (ii) N-cyclohexylmaleimide, N-phenylmaleimide, styrene, Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, Examples thereof include a copolymer with at least one selected from the group consisting of polystyrene macromonomer and polymethyl methacrylate macromonomer.

In the present invention, polystyrene conversion measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of “resin containing a structural unit derived from N-substituted maleimide” (and other resins used as necessary) The weight average molecular weight (hereinafter referred to as “Mw”) is usually 2,000 to 300,000, preferably 3,000 to 100,000.
Moreover, the number average in terms of polystyrene measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of “resin containing structural unit derived from N-substituted maleimide” (and other resins used as necessary) The molecular weight (hereinafter referred to as “Mn”) is usually 3,000 to 60,000, preferably 5,000 to 25,000.
In the present invention, the film thickness uniformity is obtained by using the copolymer A having the specific Mw and Mn, or by using the copolymer A and another resin having the specific Mw and Mn in combination. (Especially, film thickness uniformity when a pattern is formed on a substrate having a step) can be further improved. Furthermore, the developability can be further improved, whereby pixels and black matrices having sharp pattern edges can be formed. Furthermore, residues, ground stains, film residues and the like on the unexposed substrate and the light shielding layer can be more effectively suppressed during development.
The ratio of Mw to Mn (Mw / Mn) of copolymer A (and other resins used as necessary) is preferably 1 to 5, more preferably 1 to 4, respectively.

In the photosensitive resin composition of the present invention, “a resin containing a structural unit derived from an N-substituted maleimide” may be included alone or in combination of two or more. The same applies to other resins.
In the photosensitive resin composition of the present invention, the total amount of the resin is not particularly limited, but is preferably 10 to 1000 parts by mass, and more preferably 20 to 500 parts by mass with respect to 100 parts by mass of titanium black. When the total amount is 10 parts by mass or more, film thickness uniformity (particularly, film thickness uniformity when a pattern is formed on a stepped substrate) can be further improved. Furthermore, alkali developability can be further improved, and background contamination and film residue on the unexposed portion of the substrate or the light shielding layer can be further improved. Moreover, film thickness uniformity (especially film thickness uniformity when a pattern is formed on a stepped substrate) can be further improved when the content is 1000 parts by mass or less. Furthermore, the color density can be further improved.
Moreover, 10-100 mass% is preferable from the viewpoint of obtaining the effect by this invention more effectively, and, as for the usage-amount of the copolymer A in resin, 20-100 mass% is more preferable.

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

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

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

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

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

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

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

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

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, A photosensitive resin composition having an excellent photosensitive speed can be obtained.

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

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

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

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

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a 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-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) Minophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine,

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

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

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

  In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123) manufactured by Midori Chemical, T manufactured by PANCHIM Series (for example, T-OMS, T-BMP, TR, TB), Irgacure series (for example, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Ciba Specialty Chemicals) Irgacure 819, Irgacure 261), Darocur series (eg Darocur 1173), 4,4′-bis (diethylamino) -benzophenone, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2,2-dimethoxy-2- Phenyl Acetophenone,

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

The oxime compound (hereinafter also referred to as “oxime photopolymerization initiator”) is not particularly limited, and examples thereof include Japanese Patent Application Laid-Open No. 2000-80068, WO-02 / 100903A1, and Japanese Patent Application Laid-Open No. 2001-233842. Can be used.
Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio). Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime)- 1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1, -Butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) Such as 9H- carbazol-3-yl] ethanone and the like. However, it is not limited to these.

  In the present invention, from the viewpoint of further improving the film thickness uniformity (particularly the film thickness uniformity when a pattern is formed on a stepped substrate), among the above photopolymerization initiators, oxime-based photopolymerization is initiated. Among them, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is particularly preferred. Examples of such oxime photopolymerization initiators include CGI-124 and CGI-242 (manufactured by Ciba Specialty Chemicals).

  Moreover, as an oxime system photoinitiator, from a viewpoint etc. which improve film thickness uniformity (especially film thickness uniformity when forming a pattern on a board | substrate with a level | step difference) etc., following General formula (1) (Hereinafter also referred to as “new oxime compound”) is also preferred.

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

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

The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group shown below.
Examples of the monovalent nonmetallic atomic group represented by R include an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An alkynyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent An arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, and a substituent. Good phosphinoyl group, optionally substituted heterocyclic group, optionally substituted alkylthiocarbonyl group, optionally substituted arylthiocarbonyl group, optionally substituted dialkyl 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, methylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, hexylthiocarbonyl group, octylthiocarbonyl group, decylthiocarbonyl group, octadecylthiocarbonyl group, Examples thereof include a trifluoromethylthiocarbonyl group.

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

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

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

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent.
Specifically, phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, pentalenyl group, binaphthalenyl group, Turnaphthalenyl group, Quarter naphthalenyl group, Heptaenyl group, Biphenylenyl group, Indacenyl group, Fluoranthenyl group, Acenaphthylenyl group, Aceantrirenyl group, Phenalenyl group, Fluorenyl group, Anthryl group, Bianthracenyl group, Teranthracenyl group, Quarter Anthracenyl group, anthraquinolyl group, phenanthri Group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, A trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, an obalenyl group, and the like can be given. Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

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

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

  The novel oxime compound in the present invention is represented by the following general formula (2) from the viewpoint of further improving the film thickness uniformity (particularly the film thickness uniformity when a pattern is formed on a stepped substrate). It is preferable that it is a compound.

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

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

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

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-ni Rofenashiru group, and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The novel oxime compound in the present invention is represented by the following general formula (3) from the viewpoint of further improving the film thickness uniformity (particularly the film thickness uniformity when a pattern is formed on a stepped substrate). It is preferable that it is a compound.

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

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

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

The novel oxime compound in the present invention has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm. More preferably, a material having an absorption wavelength in a wavelength region of 360 nm to 480 nm can be exemplified. In particular, those having high absorbance at 365 nm and 455 nm are preferable.
Thus, the novel oxime compound has absorption in a long wavelength region as compared with the conventional oxime compound. Therefore, when exposed with a light source of 365 nm or 405 nm, excellent sensitivity is exhibited.

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

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

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

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

A sensitizer and a light stabilizer can be used in combination with these photopolymerization initiators.
Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, and 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzylacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethylamino) ) Phenyl-p-methylstyryl ketone Examples include benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in JP-B 51-48516, and tinuvin 1130, 400. .

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

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

<Solvent>
The photosensitive resin composition of the present invention contains a solvent.
Examples of the solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone. , Cyclopentanone, 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 Ter, diethylene glycol 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, Examples include ethyl lactate.
These solvents can be used alone or in combination.
In the photosensitive resin composition of the present invention, the concentration of the solid content with respect to the solvent is preferably 2 to 60% by mass.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

≪Light-shielding color filter≫
The light-shielding color filter of the present invention is formed using the above-described photosensitive resin composition of the present invention.
Since the light-shielding color filter of the present invention is formed using the photosensitive resin composition of the present invention capable of forming a pattern having excellent film thickness uniformity on a stepped substrate, the film thickness uniformity is excellent. For this reason, it is excellent in the uniformity (in-plane uniformity) of light-shielding ability. Also, the pattern adhesion with the base on which the light-shielding color filter is formed is good.

In the present invention, the “light-shielding color filter” means a light-shielding pattern obtained by exposing and developing a photosensitive resin composition containing at least a black color material, a photopolymerizable compound, a resin, a photopolymerization initiator, and a solvent. Say. The color of the “light-shielding color filter” in the present invention may be an achromatic color such as black or gray, or a black or gray color mixed with a chromatic color.
The “light-shielding color filter” is obtained by exposing and developing a photosensitive resin composition containing at least a black color material, a photopolymerizable compound, a resin, a photopolymerization initiator, and a solvent. Alternatively, it may be paraphrased as a light shielding filter.
For example, in a solid-state imaging device, the light-shielding color filter is used to shield light other than the light receiving portion on the light receiving element forming surface, to shield light on the surface opposite to the light receiving element forming surface, and color adjustment pixels (black, The pixel may be an achromatic pixel such as gray, or may be a pixel such as black or gray mixed with a chromatic color).

The film thickness of the light-shielding color filter is not particularly limited, but is preferably 0.1 μm to 10 μm, more preferably 0.3 μm to 5.0 μm, from the viewpoint of obtaining the effect of the present invention more effectively. 5 μm to 3.0 μm is particularly preferable.
The pattern size of the light-shielding color filter is not particularly limited, but is preferably 1000 μm or less, more preferably 500 μm or less, and particularly preferably 300 μm or less from the viewpoint of obtaining the effect of the present invention more effectively. The lower limit is not particularly limited but is preferably 1 μm.

In addition, the spectral characteristics of the light-shielding color filter of the present invention are not particularly limited, but from the viewpoint of improving the light shielding ability in the infrared region, which may be required for a solid-state imaging device, the light shielding ability between the visible region and the infrared region. From the viewpoint of balance and the viewpoint of obtaining the effect of the present invention more effectively, the ratio [OD ₁₂₀₀ / OD ₃₆₅ ] of the optical density (OD ₁₂₀₀ ) at a wavelength of ₁₂₀₀ nm to the optical density (OD ₃₆₅ ) at a wavelength of 365 nm is 0. It is preferably 5 or more and 3 or less.

  The optical density (OD) is obtained by measuring the transmittance of the obtained film using U-4100 manufactured by Hitachi High-Technologies Co., Ltd., and converting the obtained transmittance (% T) by the following formula 1 to obtain an OD value. And

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

In the present invention, the optical density at the wavelength _{λ nm} is expressed as “OD _λ ”.
Furthermore, the following conditions are suitable as the optical density of the light-shielding color filter from the viewpoint of the balance between the light-shielding ability in the visible region and the infrared region, and from the viewpoint of obtaining the effects of the present invention more effectively.
That is, [OD ₁₂₀₀ / OD ₃₆₅ ] is more preferably 1.0 or more and 2.5 or less, and particularly preferably 1.3 or more and 2.0 or less.
The optical density (OD ₁₂₀₀ ) at a wavelength of 1200 nm of the light-shielding color filter is preferably 2.5 to 10, and more preferably 4 to 10.
The optical density (OD ₃₆₅ ) at a wavelength of 365 nm of the light-shielding color filter is preferably 1 to 7, and more preferably 2 to 6.
The light density of the light-shielding color filter in the wavelength region of 900 nm to 1300 nm is preferably 2 or more, 10 or less, more preferably 2 or more and 9 or less, and particularly preferably 3 or more and 8 or less.
The ratio [OD ₉₀₀ / OD ₃₆₅ ] of the light-shielding color filter is preferably 1.0 or more and 2.5 or less, and more preferably 1.3 or more and 2.5 or less.
The ratio [OD ₁₁₀₀ / OD ₃₆₅ ] of the light-shielding color filter is preferably 1.0 or more and 2.5 or less, and more preferably 1.3 or more and 2.5 or less.
The ratio [OD ₁₃₀₀ / OD ₃₆₅ ] of the light-shielding color filter is preferably 1.0 or more and 2.3 or less, and more preferably 1.1 or more and 2.0 or less.

Since the light-shielding color filter of the present invention contains titanium black as a black pigment, the above-described spectral characteristics can be obtained more effectively.
The light-shielding color filter of the present invention can be suitably used for a solid-state image sensor such as a CCD or CMOS, and is particularly suitable for a solid-state image sensor such as a CCD or CMOS exceeding 1 million pixels.

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

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

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

  As a coating method of the photosensitive resin composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied. .

  When producing a light-shielding color filter, the coating film thickness (after drying) of the photosensitive resin composition is preferably 0.35 μm to 3.0 μm, preferably 0.50 μm to 2 from the viewpoint of resolution and developability. More preferably, it is 5 μm.

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

<Exposure process>
In the exposure step, the photosensitive layer formed in the photosensitive layer forming step is exposed and cured (in the case of exposing through a mask, only the coating film portion irradiated with light is cured).
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are preferably used, and a high-pressure mercury lamp is more preferable. The irradiation intensity is preferably 5 mJ to 3000 mJ, more preferably 10 mJ to 2000 mJ, and most preferably 10 mJ to 1000 mJ.

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

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

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

≪Solid-state imaging device≫
The solid-state imaging device according to the present invention includes the above-described light-shielding color filter according to the present invention.
Since the solid-state imaging device of the present invention includes the light-shielding color filter of the present invention having excellent uniformity of light-shielding ability, noise can be reduced and color reproducibility can be improved.
The configuration of the solid-state imaging device of the present invention is a configuration provided with the light-shielding color filter of the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. It has a light receiving element composed of a plurality of photodiodes and polysilicon constituting a light receiving area of an image sensor (CCD image sensor, CMOS image sensor, etc.), and has a light receiving element forming surface side of the support (for example, other than the light receiving part) A configuration in which the light-shielding color filter of the present invention is provided on the side opposite to the formation surface.

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

The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC). GPC uses HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation), and TSKgel, SuperHM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15 cm) as the column, eluent THF (tetrahydrofuran) was used. The conditions were as follows: the sample concentration was 0.5 mass%, the flow rate was 0.6 ml / min, the sample injection amount was 10 μl, the measurement temperature was 40 ° C., and the RI detector was used. In addition, the calibration curve is “polystyrene standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-”. It was prepared from 10 samples of “2,500”, “F-4”, “F-40”, “F-128”, and “F-700”.
The acid value of the resin was measured by the method of Section 11.1 of JIS K 5407 (1990).

[Example 1]
≪Synthesis of alkali-soluble resin≫
<Synthesis of Resin A-1>
A flask equipped with a condenser and a stirrer was charged with 3 parts of 2,2′-azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate, followed by 15 parts of methacrylic acid, 15 parts of N-phenylmaleimide, and tetrahydrofurfuryl. Charge 30 parts of methacrylate, 10 parts of styrene, 30 parts of n-butyl methacrylate and 3 parts of α-methylstyrene dimer as a molecular weight regulator, purge with nitrogen, start gently stirring, and raise the temperature of the reaction solution to 80 ° C. Then, this temperature was maintained for 5 hours for polymerization to obtain a solution of resin A-1 (resin containing a structural unit derived from N-substituted maleimide).

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

-Composition of Titanium Black Dispersion 1-
・ Gemco Co., Ltd. Titanium Black 13M-T 34 parts ・ Propylene glycol monomethyl acetate solution of benzyl methacrylate / methacrylic acid copolymer (BzMA / MAA = 70/30, Mw: 30000, solid content 40 mass%) 2 parts・ SOLPERS 36000 (Nippon Lubrizol Co., Ltd.)… 4 parts

The following component (A) was added to the obtained titanium black dispersion 1, and the mixture was stirred for 3 hours using a homogenizer at 3000 rpm. The obtained mixed solution was subjected to a dispersion treatment for 4 hours with a disperser (dispar mat GETZMANN) using 0.3 mm zirconia beads to obtain a titanium black dispersion 2.
This titanium black dispersion 2 had a viscosity of 6.0 mPa · s.

~ Ingredient (A) ~
・ Propylene glycol monomethyl acetate solution of benzyl methacrylate / methacrylic acid copolymer (BzMA / MAA = 70/30, Mw: 30000, solid content 40% by mass): 10 parts ・ Propylene glycol monomethyl ether acetate: 50 parts

(Preparation of photosensitive resin composition)
The following components were mixed to obtain a photosensitive resin composition (Sample 1).
-Composition of photosensitive resin composition (Sample 1)-
Alkali-soluble resin (resin A-1) 5 parts Dipentaerythritol hexaacrylate (polymerizable compound; compound T-1 below)
3 parts ethoxylated pentaerythritol tetraacrylate (polymerizable compound; compound T-2 below) 2 parts titanium dispersion 2 prepared above 45 parts propylene glycol monomethyl ether acetate (PGMEA) 7 parts Ethyl-3-ethoxypropionate 3 parts oxime photopolymerization initiator (compound K-1 below) 2 parts

<Preparation of Sample 2>
During the preparation of Sample 1, Sample 2 was prepared in the same manner as Sample 1 except that the resin A-1 was changed to the following resin J-1 having the same mass in the preparation of the photosensitive resin composition.

<Preparation of Sample 3>
During the preparation of Sample 1, in the preparation of Titanium Black Dispersion 1 and Titanium Black Dispersion 2, benzyl methacrylate / methacrylic acid copolymer (BzMA / MAA = 70/30, Mw: 30000) was used in the same mass as the resin. Sample 3 was prepared in the same manner as Sample 1 except that the sample was changed to A-1.

<Preparation of Sample 4>
During the preparation of Sample 3, Sample 4 was prepared in the same manner as Sample 1 except that the resin A-1 was changed to the same amount of the resin J-1 in the preparation of the photosensitive resin composition.

<Preparation of sample 5 (photosensitive resin composition using carbon black)>
(Preparation of carbon black dispersion)
First, the following composition was subjected to a high viscosity dispersion treatment with two rolls to obtain a carbon black dispersion 1. The resulting carbon black dispersion 1 had a viscosity of 70000 mPa · s.
In addition, you may knead | mix for 30 minutes with a kneader before a high-viscosity dispersion process.

~ Composition of carbon black dispersion 1 ~
・ Average primary particle size 15 nm carbon black: 16 parts ・ Propylene glycol monomethyl acetate solution of benzyl methacrylate / methacrylic acid copolymer (BzMA / MAA = 70/30, Mw: 30000, solid content: 40 mass%): 3 parts ・ Solpers 5000 (Nippon Lubrizol Corporation) 3 parts

The component (A) used in Sample 1 was added to the obtained carbon black dispersion 1, and the mixture was stirred for 3 hours using a homogenizer at 3000 rpm. The obtained mixed solution was subjected to dispersion treatment for 4 hours with a disperser (dispar mat GETZMANN) using 0.3 mm zirconia beads to obtain a carbon black dispersion 2.
The viscosity of this dispersion was 25.0 mPa · s.

(Preparation of photosensitive resin composition)
The following components were mixed to obtain a photosensitive resin composition (Sample 5).
-Composition of photosensitive resin composition (Sample 5)-
Alkali-soluble resin (resin A-1) 5 parts Dipentaerythritol hexaacrylate (polymerizable compound; compound T-1)
3 parts ethoxylated pentaerythritol tetraacrylate (polymerizable compound; compound T-2) 2 parts carbon dispersion 2 prepared above 21 parts propylene glycol monomethyl ether acetate (PGMEA) 35 parts Ethyl-3-ethoxypropionate 8 parts oxime photopolymerization initiator (compound K-1) 2 parts

<Preparation of Sample 6>
During the preparation of Sample 5, Sample 6 was prepared in the same manner as Sample 5 except that in the preparation of the photosensitive resin composition, Exemplified Resin A-1 was changed to Resin J-1 having the same mass.

<Preparation of Sample 7>
During the preparation of Sample 5, in the preparation of Carbon Black Dispersion 1 and Carbon Black Dispersion 2, propylene glycol monomethyl acetate solution of benzyl methacrylate / methacrylic acid copolymer (BzMA / MAA = 70/30, Mw: 30000, solid Sample 7 was prepared in the same manner as Sample 5 except that 40% by mass) was changed to the same amount of the resin A-1.

<Preparation of Sample 8>
During the preparation of Sample 7, Sample 8 was prepared in the same manner as Sample 7 except that in the preparation of the photosensitive resin composition, resin A-1 was changed to resin J-1 having the same mass.

<Preparation of Sample 9, Sample 10, Sample 11, and Sample 12>
In preparation of Sample 1, Sample 4, Sample 8, and Sample 5, the oxime photopolymerization initiator (compound K-1) was changed to an aminoalkylphenone photopolymerization initiator (Irgacure 369 below) of the same mass. Sample 9, Sample 10, Sample 11, and Sample 12 were prepared in the same manner as Sample 1, Sample 4, Sample 8, and Sample 5 except for the above.

<< Production of light-shielding color filter >>
(Preparation of stepped substrate 1)
A solder resist SR7200 manufactured by Hitachi Chemical Co., Ltd. is applied to a commercially available 6-inch silicon wafer to form a coating film, and the resulting coating film is subjected to pattern exposure and development. A columnar step having a depth of 10 μm and a diameter of 200 μm was regularly formed. The board | substrate 1 with a level | step difference was obtained by the above.

(Production of light-shielding color filter)
The above-mentioned sample 1 (photosensitive resin composition) is applied to the step forming surface side of the stepped substrate 1 obtained as described above using a spin coater, and pre-baked at 100 ° C. for 120 minutes to form a photosensitive layer. Formed.
Next, the obtained photosensitive layer was subjected to pattern exposure at an exposure amount of 500 mJ / cm ² through a photomask having a 3 mm square pattern (opening pattern) using an i-line stepper.
The exposed photosensitive layer was subjected to paddle development at 23 ° C. for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide. Thereafter, rinsing was performed with a spin shower, and further washing with pure water was performed to obtain a pattern (light-shielding color filter).

Further, each of Sample 2 to Sample 12 was used, and a light-shielding color filter was produced in the same manner as in the case of using Sample 1.
The thickness of the light-shielding color filter at the center of the wafer was 2.5 μm when any of Sample 1 to Sample 12 was used.

<Evaluation of film thickness uniformity>
For each of the light-shielding color filters obtained above, the thickness of the light-shielding color filter at the wafer central portion and the thickness of the light-shielding color filter at the wafer peripheral portion were measured.
The thickness was measured by observing the cross section of the wafer using a scanning electron microscope (SEM) (magnification 10,000 times). Here, the thickness of the light-shielding color filter refers to the distance in the normal direction of the wafer from the bottom of the step (silicon wafer surface) to the surface of the light-shielding color filter.
Further, the thickness was measured at 10 or more locations by changing the location in the wafer central portion and the wafer peripheral portion. Based on the obtained measurement results, average values at 10 or more locations in the wafer center and average values at 10 or more locations in the wafer periphery were calculated.

Next, the average value of the thickness at the peripheral portion of the wafer was divided by the average value of the thickness at the central portion, and the value obtained by multiplying the value by 100 was defined as the film thickness uniformity.
Under the conditions of Example 1, the film thickness uniformity is within a range of 100 ± 15, which is within a practical allowable range.

  Note that the wafer center portion refers to a portion inside a circle having a radius of 20% of the wafer radius from the wafer center point. The wafer peripheral portion refers to a portion sandwiched between a circle having a radius of 80% of the wafer radius and a circle having a radius of 95% from the center point of the wafer.

  The above results are shown in Table 1 below.

~ Description of Table 1 ~
“J-10” represents “benzyl methacrylate / methacrylic acid copolymer (BzMA / MAA = 70/30, Mw: 30000)”.
-"Resin used at the time of preparing the composition" refers to a step in which a photosensitive resin composition is prepared by adding a photosensitive component such as a photopolymerization initiator to the prepared pigment dispersion after preparing the pigment dispersion. Refers to added resin.

  As shown in Table 1, Sample 1, Sample 3, and Sample 4 containing titanium black, a photopolymerizable compound, a resin containing a structural unit derived from N-substituted maleimide, a photopolymerization initiator, and a solvent. Sample 9 and Sample 10 (particularly Sample 1, Sample 3 and Sample 4 using an oxime-based photopolymerization initiator) were excellent in film thickness uniformity. For this reason, the light-shielding color filter using these samples is excellent in the uniformity of light-shielding ability.

[Example 2]
Next, film thickness uniformity was evaluated when the type of the oxime photopolymerization initiator was changed under conditions more severe than Example 1 (conditions with a large step). Details are shown below.

<Sample 3>
Sample 3 was prepared in the same manner as in Example 1.

<Sample 13, Sample 14, Sample 15, Sample 16>
During the preparation of Sample 3, the photopolymerization initiator was the same as the preparation of Sample 3, except that the photopolymerization initiator was changed to the following compound K-2, the following compound K-3, the following compound K-4, and the following compound K-5 with the same mass. Thus, Sample 13, Sample 14, Sample 15, and Sample 16 were produced.
In addition, Compound K-3, Compound K-4, and Compound K-5 are compounds represented by the general formula (1).

≪Evaluation≫
<Production of evaluation substrate>
In the production of the “substrate 1 with a step” in the first embodiment, the depth of the step is changed to 15 μm by changing the coating condition of the solder resist SR7200. A substrate 2 with a step was produced in the same manner as the production.
A light-shielding color filter was produced on the stepped substrate 2 using Sample 3, Sample 13, Sample 14, Sample 15, and Sample 16 under the same conditions as in Example 1. The thickness of the light-shielding color filter at the center of the wafer was 2.5 μm regardless of which sample was used.
Furthermore, the film thickness uniformity was evaluated in the same manner as in Example 1.

  The above results are shown in Table 2 below.

  As shown in Table 2, Sample 14, Sample 15, and Sample 16 using the oxime photopolymerization initiator represented by the general formula (1) had particularly good film thickness uniformity. For this reason, the light-shielding color filter using these samples is particularly excellent in the uniformity of the light-shielding ability.

As mentioned above, although the example at the time of using a specific compound as a resin containing the structural unit derived from titanium black, a photopolymerizable compound, N-substituted maleimide, a photoinitiator, and a solvent was described, other than the above Even when a compound is used, the same effect as described above can be obtained.
Further, in Example 1 and Example 2, a solid-state imaging device with less noise and excellent color reproducibility is manufactured by using a solid-state imaging device substrate on which a light receiving element such as a photodiode is formed as a support. be able to.

Claims (8)

And titanium black, a photopolymerizable compound, a resin containing a structural unit derived from N- substituted maleimide, a photopolymerization initiator, and a solvent, only including,
The resin is (a) N-substituted maleimide, (b) at least one selected from the group consisting of unsaturated carboxylic acids, acid anhydrides of unsaturated carboxylic acids, and unsaturated phenol compounds, and (c) A photosensitive resin composition which is a copolymer of an unsaturated compound having a tetrahydrofuran skeleton and (d) an unsaturated compound other than (a), (b) and (c) . A titanium black, a photopolymerizable compound, a resin containing a structural unit derived from N-substituted maleimide, a photopolymerization initiator, and a solvent, wherein the titanium black has a particle size of 10 to 500 nm . Resin composition. The photosensitive resin composition according to claim 1, wherein the specific surface area of the titanium black is 20 to 100 m ² / g as measured by a BET method . Content of the said titanium black in the said photosensitive resin composition is 15-95 mass%, The photosensitive resin composition of any one of Claims 1-3. The photopolymerization initiator, the photosensitive resin composition according to any one of claims 1 to 4 is an oxime-based photopolymerization initiator. The light-shielding color filter formed using the photosensitive resin composition of any one of Claims 1-5 . A method for producing a light-shielding color filter comprising a step of applying a photosensitive resin composition according to any one of claims 1 to 5 on a support, exposing through a mask, and developing to form a pattern. . A solid-state imaging device comprising the light-shielding color filter according to claim 6 .