JP2009244408A - Photosensitive resin composition, light shielding color filter and production process therefor, and solid-state image sensor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition by which a light shielding color filter having satisfactory adhesion can be obtained, to provide the light shielding color filter formed by using the photosensitive resin composition and a production process therefor, and to provide a solid-state image sensor. <P>SOLUTION: The photosensitive resin composition containing least (A) titanium black, (B) a polymerizable compound, (C) a resin, (D) a photopolymerization initiator, and (E) an organic solvent has ≤3 wt.% water content. The light shielding color filter has a pattern formed by using the photosensitive resin composition. The solid-state image sensor is provided with the light shielding color filter. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

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

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

  The black matrix for liquid crystal display devices is mainly required to block light in the visible range, whereas the light-blocking film for solid-state imaging devices must have light blocking in the infrared region in addition to the light blocking property in the visible region. There is.

  As the light-shielding film for the solid-state imaging device, the light-shielding film disposed on the periphery of the imaging unit that is the peripheral region of the imaging unit (effective pixel region) and / or the protruding electrode on the back surface facing the surface on which the imaging unit is formed A light shielding film disposed between the two is important.

The problem to be solved by the present invention is to provide a photosensitive resin composition from which a light-shielding color filter with good adhesion can be obtained.
Moreover, the subject which this invention tends to solve is providing the light-shielding color filter formed with the said photosensitive resin composition, its manufacturing method, and a solid-state image sensor.

The above-described problems of the present invention have been solved by means described in the following <1> to <8>.
<1> A photosensitive resin composition containing at least (A) titanium black, (B) a polymerizable compound, (C) a resin, (D) a photopolymerization initiator, and (E) an organic solvent. A water content in the photosensitive resin composition is 3% by weight or less, a photosensitive resin composition,
<2> The photosensitive resin composition according to <1>, wherein the water content is 2% by weight or less,
<3> The photosensitive resin composition according to <1> or <2>, wherein the water content is 1% by weight or less,
<4> The photosensitive resin composition according to any one of <1> to <3>, including an oxime compound as the (D) photopolymerization initiator,
<5> The photosensitive resin composition according to any one of <1> to <4>, which is for a solid-state imaging device,
<6> A light-shielding color filter having a pattern formed using the photosensitive resin composition according to any one of <1> to <5>,
<7><1> thru | or <5> including the process of apply | coating the photosensitive resin composition as described in any one to a board | substrate, the process of image exposure, and the process of developing and patterning, It is characterized by the above-mentioned. Manufacturing method of shading color filter,
<8> A solid-state imaging device comprising the light-shielding color filter according to <6> or the light-shielding color filter obtained by the production method according to <7>.

By this invention, the photosensitive resin composition from which the light-shielding color filter with favorable adhesiveness was obtained was able to be provided.
In addition, according to the present invention, a light-shielding color filter formed from the photosensitive resin composition, a method for producing the same, and a solid-state imaging device can be provided.

(1) Photosensitive resin composition Although a black negative type photosensitive resin composition has long been known to be applied with carbon black, it is difficult to make a thin film from the viewpoint of its color density. Application of was difficult. On the other hand, the photosensitive resin composition using titanium black has been studied a little, but has little knowledge. In particular, application to a solid-state imaging device has hardly been studied.

  When the photosensitive resin composition is applied to a solid-state imaging device, adhesion has been a problem. As a result of intensive studies, the present inventors have found that the moisture content of the photosensitive resin composition has a great influence on the adhesion.

  The photosensitive resin composition of the present invention contains (A) titanium black, (B) a polymerizable compound, (C) a resin, (D) a photopolymerization initiator, and (E) an organic solvent. It is a photosensitive resin composition, The water content in the said photosensitive resin composition is 3 weight% or less, It is characterized by the above-mentioned. By controlling the water content to a specific amount, a titanium black-containing photosensitive resin composition capable of forming a highly adhesive film can be provided.

  The photosensitive resin composition of the present invention can be suitably used as a photosensitive resin composition for a solid-state image sensor, and is preferably used for forming a light-shielding color filter (light-shielding film) on the solid-state image sensor. be able to.

(Moisture content)
In the present invention, the water content in the photosensitive resin composition is important from the viewpoint of adhesion. The moisture content in the photosensitive resin composition is 3% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less.
The moisture content of the photosensitive resin composition can be measured by the Karl Fischer method. The Karl Fischer method is described in “(Revised 5th edition) Analytical Chemistry Handbook” (edited by the Japan Analytical Chemical Society, published by Maruzen Co., Ltd.), pages 306 to 309 and the literature cited therein.

Water is brought into the photosensitive resin composition from each component ((A) titanium black dispersion, (B) polymerizable compound, (C) resin, (D) photopolymerization initiator, (E) organic solvent, etc.). Therefore, in order to reduce the moisture content, it is preferable to reduce the moisture content of each component.
It is desirable to reduce the amount of water at the time of preparation of components (A) to (E) and the like and at the time of preparation of titanium black dispersion and the like, and it is preferable to sufficiently dehydrate each component and dispersion. Moreover, a water content can be reduced by dehydrating even after preparation of the photosensitive resin composition.

  As a dehydration method, if it is in a solution state, a method of dehydrating with a dehydrating agent such as magnesium sulfate or sodium sulfate, a method of dehydrating using molecular sieves or synthetic zeolite, and a dehydrating distillation process if it is an organic solvent. Method, etc. The method for the dehydration treatment is not limited to the method described here, as long as the water content of the obtained photosensitive resin composition is lowered.

Hereinafter, each component of the photosensitive resin composition of this invention is demonstrated. In addition, “A to B” or the like representing the numerical range is synonymous with “A or more and B or less” unless otherwise specified.
(A) Titanium black The photosensitive resin composition of the present invention contains titanium black as a black color material.
Titanium black has a higher light blocking ability in the infrared region than conventional pigments and dyes dispersed and dissolved in photosensitive resin compositions, especially color filter photosensitive resin compositions. The infrared light region can be surely shielded, which cannot be shielded by combination. In particular, the light-shielding film obtained by curing the photosensitive resin composition of the present invention has a high light-shielding property in the infrared light region, and can suppress noise due to dark current of a solid-state imaging device having the light-shielding film.
Titanium black can be cured with less exposure because it absorbs less i-rays for pattern formation compared to carbon black, which is commonly used as a black color material, and is therefore productive. It can contribute to improvement.

Titanium black is black particles having titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. The surface of the titanium black particles can be chemically modified as necessary for the purpose of improving dispersibility and suppressing aggregation. Specifically, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and as disclosed in Japanese Patent Application Laid-Open No. 2007-302836. Surface treatment with a water repellent material is also possible.
In addition, the titanium black is a composite oxide such as Cu, Fe, Mn, V, and Ni, and a black pigment such as cobalt oxide, iron oxide, carbon black, and aniline black for the purpose of adjusting dispersibility, colorability, and the like. You may contain 1 type or in combination of 2 or more types.
In addition, for the purpose of controlling the light-shielding property of a desired wavelength, it is also possible to add existing colorants such as pigments such as red, blue, green, yellow, cyan, magenta, violet, orange, or dyes. .

  Examples of commercially available titanium black products include Gemco Corporation (sold by Mitsubishi Materials Corporation) Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T, and Ako Kasei. Tilac D manufactured by Co., Ltd. and the like can be mentioned.

  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, JP-A-61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at a high temperature in the presence of ammonia (JP-A-61-201610), and the like. It is not something.

  The particle size of the titanium black particles is not particularly limited, but the average particle size (average primary particle size) is 10 to 150 nm from the viewpoints of dispersibility and colorability and the influence on the yield in a solid-state imaging device. It is preferable that it is, it is more preferable that it is 50-100, and it is especially preferable that it is 80-100 nm. The average particle diameter can be measured by applying titanium black to a suitable substrate and observing with a scanning electron microscope.

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, and therefore the value measured by the BET method is 5 to 150 m ^2. / G is preferable, and 20 to 100 m ² / g is more preferable.

In the present invention, titanium black and other black color materials may be used in combination, and black color materials other than titanium black may be used alone or in combination of two or more.
As the black color material that can be used in combination, various known black pigments and black dyes can be used.In particular, carbon black, iron oxide, manganese oxide, graphite and the like are preferable from the viewpoint of realizing a high optical density in a small amount, Among these, carbon black is 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 1,000 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 resin, 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 manufactured by Mitsubishi Chemical Corporation. # 850, MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45 # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond black N234, diamond black I, diamond black LI, diamond black II, die Black N339, Diamond Black SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LP . Carbon black thermax N990, N991, N907, N908, N990, N991, N908 made by Cancarb. Asahi Carbon Co., Ltd. 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 Fw2V, ColorBlack Fw1, ColorBlack 170 Black Black, Color Black 170 , ColorBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, PrintexU, PrintexV, Printex140U, Printex1 Mention may be made of 0V and the like.

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. This insulating property is based on the fact that an organic compound is present on the surface of the carbon black particle, for example, an organic substance is adsorbed, coated or chemically bonded (grafted) on the surface of the carbon black particle.
That is, carbon black was dispersed and applied in propylene glycol monomethyl ether acetate such that benzyl methacrylate and methacrylic acid had a molar ratio of 70:30 copolymer (weight average molecular weight 30,000) and 20:80 weight ratio. A liquid is prepared and applied onto a chrome substrate having a thickness of 1.1 mm and 10 cm × 10 cm to produce a coating film having a dry film thickness of 3 μm. The coating film is then heated on a hot plate at 220 ° C. for about 5 minutes. After that, it is applied with a high resistivity meter manufactured by Mitsubishi Chemical Corporation conforming to JISK6911 and Hirestar UP (MCP-HT450), and the volume resistance value is measured in an environment of 23 ° C. and 65% relative humidity. The volume resistance value of carbon black is preferably 10 ⁵ Ω · cm or more, more preferably 10 ⁶ Ω · cm or more, and particularly preferably 10 ⁷ Ω · cm or more.

  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 average particle diameter (average primary particle diameter) of the black color material used in combination with titanium black 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 diameter is preferably 10 to 100 nm, more preferably 50 nm or less, and preferably 30 nm or less.
The average particle diameter can be measured by applying a black color material to a suitable substrate and observing with a scanning electron microscope.

The content of titanium black in the photosensitive resin composition is not particularly limited, but the average transmittance in the visible region to infrared region (400 to 1,600 nm) of the light-shielding color filter to be formed is 1. % Or less is preferable. It is preferable that an optical density of 2.0 or more is obtained with substantially the same film thickness as a color separation filter such as RGB.
The blending amount of titanium black in the solid content contained in the photosensitive resin composition is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, further preferably 10 to 60% by weight, and 20 to 40% by weight. Is particularly preferred. An appropriate optical density is obtained within the above numerical range.

The content of the black colorant composed of titanium black and other black color material in the photosensitive resin composition is not particularly limited, but is preferably as high as possible in order to obtain a high optical density in the thin film, 5 to 95% by weight is preferable, 10 to 95% by weight is more preferable, and 10 to 85% by weight is particularly preferable.
If it is within the above numerical range, it is not necessary to increase the film thickness to obtain a high optical density, and photocuring proceeds sufficiently, so that the strength as a film is appropriate, and the development latitude during alkali development is appropriate. Is preferable without narrowing.

When titanium black and other black color material are used in combination, the preferred weight ratio of titanium black: other black color material is 95: 5 to 60:40, more preferably 95: 5 to 70:30. More preferably, it is 90: 10-80: 20. In addition, when there are several other black color materials used together with titanium black, it is preferable to make those total weight into said range.
By making the weight ratio of titanium black and other black color materials within the above range, the dispersibility in the photosensitive resin composition becomes good, and a stable coating film without unevenness can be formed, which is preferable.

  In addition, a dispersant having an acid value / amine value can be used for the dispersion of the above-described titanium black or carbon black. Specifically, Solsperse 5000, Solsperse 24000, Solsperse 33500, and Big DispersBYK161 manufactured by Chemie Japan Co., Ltd. can be used. Here, “having an acid value / amine value” means having a group having an acid value, having a group having an amine value, or having both.

In addition, as other dispersants, homopolymer polymers or copolymer polymers obtained by polymerizing monomers such as (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamide or derivatives thereof, styrene or derivatives thereof, etc. Can be used.
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 Methacrylic monomers such as dodecyl acid, benzyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate; ethylene, propylene, butylene, vinyl chloride, vinyl acetate, acrylonitrile, acrylamide, methacryl Examples thereof include homopolymers or copolymers of various monomers such as amide and N-vinylpyrrolidone. Of these, (meth) acrylic acid ester-based polymers are preferable.

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

  The resin used as the dispersant is not limited in molecular weight as long as dispersibility can be ensured, but from the viewpoint of dispersibility, the weight average molecular weight is preferably 500 to 200,000, more preferably 800 to 50,000, and still more preferably 1. , 30,000 to 30,000.

  As a dispersion medium for dispersing other black color materials such as titanium black and carbon black, various water-soluble or water-insoluble materials can be used as long as they can function as a solvent for dispersion. Alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and allyl alcohol; ethylene glycol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol, polyethylene glycol, polypropylene glycol, diethylene glycol monoethyl ether, polypropylene glycol monoethyl ether, polyethylene Glycols such as glycol monoallyl ether and polypropylene glycol monoallyl ether or derivatives thereof; glycerol, Theroux 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 demnum (manufactured by Daikin Industries, 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.

When preparing a black color material dispersion containing titanium black in the present invention, the polymer component is preferably added in an amount of 5 to 200 parts by weight, more preferably 10 to 100 parts by weight per 100 parts by weight of the black color material. To do.
When the polymer component is 5 parts by weight or more, the surface property of the black color material can be kept better, and when the polymer component is 200 parts by weight or less, the inherently required black color such as light-shielding property and coloring property The characteristics of the material can be further improved.

  The photosensitive resin composition of the present invention includes pigments such as red, blue, green, yellow, cyan, magenta, violet, orange and the like for the purpose of controlling the light-shielding property at a desired wavelength in addition to the black color material described above. Alternatively, a known colorant such as a dye can be added.

(B) Polymerizable compound The photosensitive resin composition of the present invention contains a polymerizable compound. This polymerizable compound is preferably a compound that undergoes addition polymerization by the action of a photopolymerization initiator. As the polymerizable compound, an ethylenically unsaturated compound having at least one ethylenically unsaturated bond in the molecule is preferably used.
As the polymerizable compound, a polyfunctional ethylenically unsaturated compound having two or more terminal ethylenically unsaturated bonds is more preferable. 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, dimers, trimers and oligomers, or mixtures thereof. The polymerizable compound preferably has a molecular weight of 70 to 2,000, and more preferably 100 to 1,000.

  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 hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional A dehydration-condensation reaction product with 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 Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group with monofunctional or polyfunctional alcohols, amines or thiols. 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, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are 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 No. 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 vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following formula (A) to a polyisocyanate compound having two or more isocyanate groups. Etc.

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

  Further, urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56-17654 And urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418. Furthermore, 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 are used. Depending on the case, it is possible to obtain a photosensitive resin composition having an extremely excellent photosensitive speed.

  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. In addition, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid-based compounds described in JP-A-2-25493 are also included. Can do. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, 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 content of ethylenically unsaturated groups 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 furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid esters, methacrylic acid esters, styrene compounds, vinyl ether compounds). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.

  In addition, selection and use of polymerizable compounds is important for compatibility and dispersibility with other components (eg photopolymerization initiator, titanium black, resin, etc.) contained in the photosensitive resin composition. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving adhesion to a hard surface such as a substrate.

  When using 2 or more types of polymeric compounds together, it is preferable to use together 2 or more types of ethylenically unsaturated compounds from which the number (functional number) of ethylenically unsaturated groups which exist in 1 molecule differs.

  In the present invention, it is more preferable to use ethylenically unsaturated compounds having different functional numbers selected from 2 to 6 functional groups, and 4 to 6 functional (meth) which is a complete (meth) acrylic acid ester of an aliphatic polyol. It is more preferable to use two kinds of acrylic acid esters in combination.

  The content of the polymerizable compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, particularly 5 to 30% by weight, based on the total solid content (weight) of the photosensitive resin composition. preferable.

(C) Resin The photosensitive resin composition of the present invention contains a resin as a binder (film forming agent). This resin is preferably an alkali-soluble resin. The alkali-soluble resin is not particularly limited as long as it is water-soluble or alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

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

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

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic esters having an aliphatic hydroxyl group such as methacrylic esters.
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Acrylic acid having no aliphatic hydroxyl group such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate, etc. Esters.

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Methacrylic acid having no aliphatic hydroxyl group such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, propargyl methacrylate Esters.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

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

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. Examples thereof include compounds described in JP-A Nos. 2002-309057 and 2002-311569.

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

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

  In the present invention, among the resins described above, a resin having a monomer unit having a polymerizable group and a monomer unit having an acidic group is preferred. The monomer unit having a polymerizable group is preferably a monomer unit having an ethylenically unsaturated group, and more preferably a monomer unit having an acryloyloxy group or a methacryloyloxy group in the side chain. As the monomer unit having an acidic group, a monomer unit having a sulfonic acid group or a carboxy group is preferable, and a monomer unit derived from acrylic acid or methacrylic acid is preferable.

As a weight average molecular weight of resin contained in the photosensitive resin composition in the present invention, a polymer of 1,000 to 200,000 is preferable, a polymer of 2,000 to 100,000 is more preferable, and 5,000 to A polymer of 50,000 is particularly preferred.
The number average molecular weight is preferably greater than 2,000, and more preferably in the range of 3,000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.
These resins may be any of random polymers, block polymers, graft polymers and the like.

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

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

(D) 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 photopolymerize the polymerizable compound, but is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
The photopolymerization initiator that can be used in the present invention is a compound that absorbs actinic radiation (light) and generates a polymerization initiating species. Examples of the active radiation include γ rays, β rays, electron beams, ultraviolet rays, visible rays, and infrared rays.

  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, and oxime compounds.

  Examples of the halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound described in JP-B-57-6096, 2-trichloromethyl-5-styryl-1, and the like. , 3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3 , 4-oxadiazole and the like.

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

  Specific examples of the halomethyl-s-triazine compound include 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-methoxynaphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, -(4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-butoxynaphth-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-methoxynaphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (6-methoxy-5- Methylnaphth-2-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (6-methoxynaphth-2-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (5-methoxynaphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4,7-dimethoxynaphth-1-yl) -4,6-bis (trichloromethyl)- s-triazine, 2- 6-Ethoxynaphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxynaphth-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 (tri Roromechiru) -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 (tri Roromechiru) -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) Chloroethyl aminophenyl) -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 Co., Ltd., manufactured by PANCHIM T series (for example, T-OMS, T-BMP, T-R, TB), Irgacure series (for example, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure, manufactured by Ciba Specialty Chemicals) 149, Irgacure 819, Irgacure 261), Darocur series (eg Darocur 1173), 4,4′-bis (diethylamino) benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1 , 2-octanedione, -(O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2, 2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- ( o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl Dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmerca) Tofeniru) -4,5-diphenyl imidazolyl dimer, can benzoin isopropyl ether also preferably used.

As the photopolymerization initiator, a compound having no halogen atom is preferable, and an initiator having high sensitivity to i-line is preferable. Examples thereof include lophine dimers and oxime compounds. As the oxime compound, an oxime ester compound is more preferable.
Among the oxime photopolymerization initiators, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is preferred.
Further, as the oxime photopolymerization initiator, a compound represented by the following formula (1) (hereinafter also referred to as “specific oxime compound”) is preferable. The specific oxime compound is a mixture of the (E) isomer and the (Z) isomer, regardless of whether the oxime N—O bond is an (E) oxime compound or a (Z) oxime compound. It may be.

（式（１）中、Ｒ及びＢは各々独立に一価の置換基を表し、Ａは二価の有機基を表し、Ａｒはアリール基を表す。）

(In 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.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Phosphinoyl group, heterocyclic group, alkylthiocarbonyl group, arylthiocarbonyl group, dialkylaminocarbonyl group, dialkylaminothiocarbonyl group and the like. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryloxy groups such as phenoxy group and p-tolyloxy group. , Methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group or aryloxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, Acyl groups such as methacryloyl group and methoxalyl group, alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group, arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group, Group, alkylamino group such as cyclohexylamino 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, In addition to alkyl groups such as tert-butyl group and 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 group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphono group, trimethylammonium group, dimethylsulfonium group, triphenyl Phenacylphosphonium group And the like.

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

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, specifically, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-anthryl group. 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, Xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, ASEAN Trirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, ter Nthracenyl group, quarteranthracenyl 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, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and specific examples include a vinyl group, an allyl group, and a styryl group.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and specific examples 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, and specifically includes a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, and a butylsulfinyl group. Group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, and methoxymethylsulfinyl group. .

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, and specifically includes 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-nitro Phenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenol Rusurufiniru group, and a 4-dimethylaminophenyl sulfinyl group can be exemplified.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specifically includes a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group. Group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, and perfluoro An alkylsulfonyl group can be illustrated.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specifically includes a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, 2- Chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitro Phenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, and 4-dimethyl Aminophenyl sulfonyl group can be exemplified.

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

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

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

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, specifically, a dimethylphosphinoyl group, a diethylphosphinoyl group, a dipropylphosphinoyl group, or diphenyl. Examples include phosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, and bis (2,4,6-trimethylphenyl) phosphinoyl group.

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

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

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

  Specific examples of the dialkylaminocarbonyl group 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, as R, an acyl group is more preferable, and specifically, an acetyl group, a propanoyl group, a benzoyl group, and a toluoyl group are more preferable.

The monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
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 formula (2) described later, and preferred examples are also the same.

Examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A 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. Examples of the substituent include the above-described substituents.
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, pentarenyl group, binaphthalenyl group, turnaphthalenyl group , Quarternaphthalenyl group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracene Nyl group, anthraquinolyl group, phenanthryl group Triphenylenyl group, pyrenyl group, chrycenyl group, naphthacenyl group, pleiadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentaphenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, trinaphthylenyl group , A heptaphenyl group, a heptacenyl group, a pyrantrenyl group, and an oberenyl group.
Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

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

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

（式（２）中、Ｒ及びＸは各々独立に一価の置換基を表し、Ａ及びＹは各々独立に二価の有機基を表し、Ａｒはアリール基を表し、ｎは０〜５の整数である。）

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

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

  Examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, and an arylsulfinyl group. Group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, amino group, phosphinoyl group, heterocyclic group and halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

  The alkyl group, aryl group, alkenyl group, alkynyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, phosphinoyl group, and heterocyclic ring in X The group is an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group of R in the formula (1). , Phosphinoyl group and heterocyclic group, and the preferred range is also the same.

  The alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms, specifically, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, or a tert-butoxy group. Pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, dodecyloxy, octadecyloxy, ethoxycarbonylmethyl, 2-ethylhexyloxycarbonylmethyl Oxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarbonylmethyloxy group Group, N- methyl -N- benzylaminocarbonyl methyl group, a benzyl group, and a cyano methyl group can be exemplified.

  The aryloxy group is preferably an aryloxy group having 6 to 30 carbon atoms, and specifically includes a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, and 2-methylphenyloxy. Group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group, 4-fluorophenyloxy Group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, and 4-phenylsulfanylphenyloxy group.

  As the acyloxy group, an acyloxy group having 2 to 20 carbon atoms is preferable. Specifically, an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, a trifluoromethylcarbonyloxy group, a benzoyloxy group , 1-naphthylcarbonyloxy group, and 2-naphthylcarbonyloxy group.

  As the alkylsulfanyl group, an alkylsulfanyl group having 1 to 20 carbon atoms is preferable. Specifically, a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a cyclohexylsulfanyl group. Octylsulfanyl group, 2-ethylhexylsulfanyl group, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, and methoxymethylsulfanyl group.

  The arylsulfanyl group is preferably an arylsulfanyl group having 6 to 30 carbon atoms, and specifically includes a phenylsulfanyl group, a 1-naphthylsulfanyl group, a 2-naphthylsulfanyl group, a 2-chlorophenylsulfanyl group, and 2-methylphenylsulfanyl. Group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group, 4-fluorophenylsulfanyl group A group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfanyl group, and 4-dimethylamino-phenylsulfanyl group can be exemplified.

  The carbamoyl group is preferably a carbamoyl group having 1 to 30 carbon atoms, specifically, an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, an N-butylcarbamoyl group, or an N-hexylcarbamoyl group. 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-cyanophenylcarbamoyl group, N- 4-metoki Phenylcarbamoyl 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.

  As the sulfamoyl group, a sulfamoyl group having 0 to 30 carbon atoms is preferable, and specifically, a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, an N, N-dialkylsulfamoyl group. , N, N-diarylsulfamoyl group and 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 Preferred examples include a group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, and N, N-diphenylsulfamoyl group.

The amino group is preferably an amino group having 0 to 50 carbon atoms, and specifically includes an amino group (—NH ₂ ), an N-alkylamino group, an N-arylamino group, an N-acylamino group, and an N-sulfonyl group. Examples include an amino group, an N, N-dialkylamino group, an N, N-diarylamino group, an N-alkyl-N-arylamino group, and an N, N-disulfonylamino group. 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) An amino group, an N, N- (dibutylsulfonyl) amino group, an N, N- (diphenylsulfonyl) amino group, a morpholino group, and 3,5-dimethyl-morpholino group, a carbazole group can be preferably exemplified.

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

Among these, X is an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkylsulfanyl group, an arylsulfanyl group, from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region, An amino group is preferred.
Moreover, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

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

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

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

（式（３）中、Ｒ及びＸは各々独立に一価の置換基を表し、Ａは二価の有機基を表し、Ａｒはアリール基を表し、ｎは０〜５の整数である。）

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

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

  Specific examples (K-1) to (K-88) of the specific oxime compound in the present invention are shown below, but the present invention is not limited thereto.

  The specific oxime compound in the present invention has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and has high absorbance at 365 nm and 455 nm. Is particularly preferred. In particular, since the specific oxime compound has an absorption in a long wavelength region as compared with a conventional oxime compound, it exhibits excellent sensitivity when exposed to a light source of 365 nm or 405 nm.

The specific oxime compound in the present invention preferably has a molar extinction coefficient at 365 nm or 405 nm of 10,000 to 300,000, more preferably 15,000 to 300,000, from the viewpoint of sensitivity. 000 to 200,000 is particularly preferable.
In the present invention, a known method can be used for the molar extinction coefficient of the compound. Specifically, for example, in an ultraviolet-visible spectrophotometer (Vary Inc., Carry-5 spectrophotometer), an ethyl acetate solvent is used. Is preferably measured at a concentration of 0.01 g / L.
In the present invention, the specific oxime compound is preferably an oxime ester compound.

  Although the specific oxime compound in this invention is compoundable by the method shown below, for example, it is not limited to this method.

Moreover, the photosensitive resin composition of this invention can use a sensitizer and a light stabilizer together.
Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, and 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzylacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethylamino) ) Phenyl-p-methylstyryl ketone Examples include benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, and tinuvin 1130, 400. .

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

The photosensitive resin composition of this invention may contain only 1 type of photoinitiators, or may contain 2 or more types.
From the viewpoint of more effectively obtaining the effects of the present invention, 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 1 to 30% by weight is preferable, 2 to 25% by weight is more preferable, and 3 to 20% by weight is particularly preferable.

(E) Organic solvent The photosensitive resin composition of the present invention contains an organic solvent. The organic solvent used in the present invention is not particularly limited as long as it satisfies the solubility of each component (A) to (D) and the coating characteristics of the photosensitive resin composition, but in particular (A) dispersibility of titanium black, (C) It is preferable to select the combination in consideration of the solubility, applicability, and safety of the resin.

  Usable solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

  3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

  Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc .;

  Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone are preferred; aromatic hydrocarbons such as toluene and xylene are preferred.

Any of these organic solvents preferably has a boiling point in the range of 100 to 180 ° C., more preferably in the range of 120 to 160 ° C. at normal pressure.
Of these, propylene glycol monomethyl ether acetate (boiling point 146 ° C.) is preferred.

(F) Other components The photosensitive resin composition of this invention may contain (F) other components in addition to said (A)-(E). (F) As other components, a crosslinking agent, a sensitizer, a strong sensitizer, a thermal polymerization inhibitor, an adhesion improver, and other additives can be exemplified.

<Crosslinking agent>
In the present invention, it is also possible to obtain a film that is further cured by using a crosslinking agent. Hereinafter, the crosslinking agent will be described.
The crosslinking agent that can be used in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. At least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with at least one substituent selected from Substituted phenol compounds, naphthol compounds or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are preferred.

  The epoxy resin (a) may be any epoxy resin as long as it has an epoxy group and has crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. , Hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diphthalic acid diglycidyl ester, N, N-diglycidyl aniline and other divalent glycidyl group-containing low molecular weight compounds, as well as trimethylolpropane triglycidyl ether, Trivalent glycidyl group-containing low molecular weight compounds represented by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc., as well as pentaerythritol tetraglycidyl ether, tetramethylol vinyl Tetravalent glycidyl group-containing low molecular weight compounds typified by phenol A tetraglycidyl ether, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, polyglycidyl ( And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 for melamine compounds, 2 for glycoluril compounds, guanamine compounds, and urea compounds. Although it is -4, Preferably it is 5-6 in the case of a melamine compound, and is 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.
Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of (b) are collectively referred to as a compound (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group) according to (b).

  The methylol group-containing compound according to (b) can be obtained by heating the alkoxymethyl group-containing compound according to (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound according to (b) is obtained by mixing and stirring the methylol group-containing compound according to (b) with an acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compound according to (b) having the substituent will be given.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

  Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine, or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol. Examples thereof include compounds obtained by acyloxymethylating 1 to 3 methylol groups of guanamine or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds in which 1 to 3 are acyloxymethylated or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
These compounds according to (b) may be used alone or in combination.

  The crosslinking agent (c), that is, a phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is the crosslinking agent ( Similar to the case of b), the thermal cross-linking suppresses intermixing with the overcoated photoresist and further increases the film strength. Hereinafter, these compounds may be collectively referred to as a compound according to (c) (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinking agent (c) is at least 2 per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

The methylol group-containing compound according to the above (c) uses a compound in which the phenolic OH group is a hydrogen atom at the 2nd or 4th position as a raw material, and this is used as sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium hydroxide. It can be obtained by reacting with formalin in the presence of a basic catalyst.
The alkoxymethyl group-containing compound according to (c) can be obtained by heating the methylol group-containing compound according to (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like.
The acyloxymethyl group-containing compound according to (c) can be obtained by reacting the methylol group-containing compound according to (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeleton compound in the crosslinking agent (c) include phenol compounds, naphthols, hydroxyanthracene compounds, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

  Specific examples of the crosslinking agent (c) include, as a phenol compound, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol- Compounds obtained by methoxymethylating one or two methylol groups of 3-cresol, tri (methoxymethyl) -3-cresol, trimethylol-3-cresol, dimethylol cresol such as 2,6-dimethylol-4-cresol, Compounds obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4 ′ Bishydroxybiphenyl, hexamethylol form of TrisP-PA, hexamethoxymethyl form of TrisP-PA, compound obtained by methoxymethylating 1 to 5 methylol groups of the hexamethylol form of TrisP-PA, bishydroxymethylnaphthalenediol, etc. Is mentioned.

  Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene, and examples of the acyloxymethyl group-containing compound include, for example, a part of the methylol group of the methylol group-containing compound. Examples include compounds that are all acyloxymethylated.

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds according to (c) may be used alone or in combination.

  The total content of the crosslinking agent in the photosensitive resin composition is preferably 1 to 70% by weight, more preferably 5 to 50% by weight, and more preferably 7 to 30% based on the solid content (weight) of the photosensitive resin composition. Weight percent is particularly preferred.

<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 polymerizable 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 weight 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 about 0.5 to about 10% by weight of the total composition.

<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), square Ums (eg, squalium), acridine orange, coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzene , Carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, etc. And aromatic ketone compounds, and heterocyclic compounds such as N-aryloxazolidinones.

  When the photosensitive resin composition of the present invention contains a sensitizer, the content of the sensitizer in the photosensitive resin composition is the total solid content from the viewpoint of light absorption efficiency to the deep part and starting decomposition efficiency. It is preferable that it is 0.1-20 weight% with respect to a weight, and 0.5-15 weight% 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 polymerization inhibition of the polymerizable 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. Is preferably in the range of 0.1 to 30% by weight, more preferably in the range of 1 to 25% by weight, and still more preferably in the range of 0.5 to 20% by weight.

<Adhesion improver>
In the photosensitive resin composition of this invention, in order to improve adhesiveness with hard surfaces, such as a board | substrate, 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 weight in the total solid content of the photosensitive resin composition, and 0.7 to 20 Weight percent is more preferred.

<Other additives>
Furthermore, in order to improve the physical properties of the cured film, known additives such as an inorganic filler, a plasticizer, and a sensitizer may be added to the photosensitive resin composition of the present invention.
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, and the like. 10% by weight or less can be added.

(Method for producing photosensitive resin composition)
The photosensitive resin composition of the present invention can be prepared by mixing the components (A) to (E) and, if necessary, (F) other components and uniformly dispersing titanium black. .
Titanium black is preferably dispersed in advance in the resin solution in the presence of a dispersion aid. The step of dispersing titanium black is preferably performed in two stages: a step of kneading in a highly viscous resin solution and a step of dispersing the media using a medium.

In the kneading step of titanium black in the production of the photosensitive resin composition of the present invention, first, titanium black and other combined black color material, a dispersant and / or a surface treatment agent, an alkali-soluble resin, and a solvent are kneaded. It is preferable. The machine used for the kneading is not particularly limited, but examples include a two-roll, a three-roll, a ball mill, a tron mill, a disper, a kneader, a kneader, a homogenizer, a blender, and a single-screw or twin-screw extruder, and a strong shearing force. It is preferable to disperse while giving.
Next, an organic solvent and a resin (the remainder used in the kneading step) are added. Examples of the machine used in the dispersion process include vertical or horizontal sand grinders, pin mills, slit mills, and ultrasonic dispersers. Media (beads) such as glass and zirconia having a particle diameter of 0.1 to 1 mm It is preferable to disperse using.
It is possible to omit the kneading step. In that case, it is preferable to disperse the pigment, the dispersant and / or the surface treatment agent, the resin, and the solvent in a medium. In this case, it is preferable to add the remaining resin in the kneading step during the dispersion.
For details of the kneading step and the dispersing step, see T.W. C. By Patton, “Paint Flow and Pigment Dispersion” (1964, John Wiley and Sons) and the like.

(2) Light-shielding color filter The photosensitive resin composition of this invention can be preferably used for manufacture of a light-shielding color filter.
In the present invention, the “light-shielding color filter” is obtained by coating, exposing and developing a photosensitive resin composition containing at least a black color material, a polymerizable compound, a resin, a photopolymerization initiator, and an organic solvent. This refers to the light-shielding pattern. 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 coating, exposing and developing a photosensitive resin composition containing at least a black color material, a photopolymerizable compound, a resin, a photopolymerization initiator, and an organic solvent. In other words, the term “light-shielding film” or “light-shielding filter” may be used.

The light-shielding color filter means a filter having an average transmittance of 10% or less in the visible region and infrared region (400 to 1,600 nm), and preferably has an average transmittance of 1% or less.
It is preferable that the light-shielding color filter is provided in the light-shielding portion on the back surface facing the surface where the imaging unit periphery of the solid-state imaging device is located and / or the surface where the imaging unit is located.
By increasing the light shielding property of the imaging unit peripheral edge light shielding unit and / or the imaging surface back surface, the dark current generated outside the imaging unit is reduced, and the photoelectric conversion function through the color filter arranged in the imaging device is improved. be able to.

In the present invention, the optical density of the light-shielding color filter formed using the photosensitive resin composition is preferably 2 to 10, more preferably 3 to 10, and 4 to 9. It is particularly preferred.
The film thickness of the light-shielding color filter of the present invention is not particularly limited, but is preferably 0.1 to 10 μm and more preferably 0.3 to 5.0 μm from the viewpoint of obtaining the effect of the present invention more effectively. 0.5 to 3.0 μm is particularly preferable.
The size (length of one side) of the light-shielding color filter of the present invention is not particularly limited, but is preferably 200 μm or more, more preferably 500 μm or more, from the viewpoint of obtaining the effect of the present invention more effectively, 000 μm or more is particularly preferable. The upper limit is not particularly limited, but is preferably 3,000 μm or less.
Further, the area of the light-shielding color filter of the present invention is not particularly limited, but from the viewpoint of more effectively obtaining the effect of the present invention, 0.05 mm ² or more is more preferable, and 0.2 mm ² or more is more preferable. 1 mm ² or more is particularly preferable. The upper limit is not particularly limited, but 9 mm ² is preferable.

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

(3) Manufacturing method of light-shielding color filter Although the manufacturing method of the light-shielding color filter of this invention is not specifically limited, (a) The process (photosensitive layer formation) of apply | coating the photosensitive resin composition of this invention to a board | substrate. It is preferable to include a step), (b) a step of image exposure (exposure step), and (c) a step of developing and patterning (development step).
Hereinafter, each process in the manufacturing method of the light-shielding color filter of this invention is demonstrated.

(A) Photosensitive layer forming step In the photosensitive layer forming step, the photosensitive resin composition of the present invention is applied onto a substrate to form a photosensitive layer.
Examples of the substrate 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, on these substrates, if necessary, an undercoat layer may be provided to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface of the substrate.

As a coating method of the photosensitive resin composition of the present invention on the substrate, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied.
The coating thickness of the photosensitive resin composition is preferably 0.35 μm to 3.0 μm and more preferably 0.50 μm to 2.5 μm from the viewpoint of resolution and developability.

  The photosensitive resin composition coated on the substrate is usually dried at 70 ° C. to 110 ° C. for about 2 minutes to 4 minutes to form a photosensitive layer.

(B) Exposure process In an exposure process, the photosensitive layer formed in the said photosensitive layer formation process is exposed and hardened. In the present invention, the exposure step is preferably a step of exposing through a mask, and more preferably a step of exposing through a photomask. In addition, when exposing through a mask, it is preferable to harden only the coating film part irradiated with light.
The exposure is preferably performed by irradiation with radiation, and as radiation that can be used for the exposure, ultraviolet rays such as g-line (436 nm) and i-line (365 nm) are particularly preferably used, and i-line is more preferably used. A high pressure mercury lamp is more preferred as the light source. The irradiation intensity is preferably 5 to 1,500 mJ, more preferably 10 to 1,000 mJ, and most preferably 10 to 800 mJ.

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

  Examples of the alkali used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0. ] An alkaline aqueous solution obtained by diluting an organic alkaline compound such as -7-undecene with pure water so as to have a concentration of 0.001 to 10% by weight, preferably 0.01 to 1% by weight. 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 for the solid-state imaging device of the present invention, the formed pattern is heated as necessary after the photosensitive layer forming step, the exposure step, and the development step. And / or the hardening process hardened | cured by exposure may be included.
The heating step (post-bake treatment) after the development step is heating after development for complete curing, and heating at 180 to 250 ° C. (hard baking) is preferable. This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like so that the coating solution after development is in the above temperature condition. be able to.
In addition to the post-baking treatment or independently, the colored pattern may be cured by irradiating ultraviolet rays with a high-pressure mercury lamp or the like (post-cure treatment).

(4) Solid-state image sensor The photosensitive resin composition of this invention can be preferably used for solid-state image sensors. Specifically, after coating the photosensitive resin composition of the present invention as a thin film on a substrate, image exposure with i-line or the like, development and patterning make it a light-shielding color having a desired shape A filter can be manufactured.
As already described, the light-shielding color filter means a filter having an average transmittance of 10% or less in the visible region and the infrared region (400 to 1,600 nm), and the average transmittance is It is preferable that it is 1% or less.
A solid-state imaging device according to the present invention includes the light-shielding color filter described above.
Hereinafter, the solid-state imaging device will be described with reference to the drawings.

FIG. 1 is a cross-sectional view illustrating an example of an imaging unit of a solid-state imaging device according to the present invention and a light shielding unit arranged at the periphery thereof. FIG. 1 shows an example of a solid-state imaging device having a light-shielding color filter obtained by photocuring the solid content of the photosensitive resin composition of the present invention at the periphery of the color filter constituting the three primary color pixels.
In FIG. 1, the solid-state imaging device 1 includes a photoelectric conversion element (light receiving sensor unit) 12 on a silicon substrate 10. Further, transfer electrodes (14 a, 14 b) for transferring the generated charges are provided adjacent to the photoelectric conversion element 12. The transfer electrodes 14 a and 14 b are covered with an insulating film 16.
A color filter (4R, 4G, 4B) in which three primary color pixels composed of the three primary colors of R (red), G (green), and B (blue) are regularly arranged is disposed on the photoelectric conversion element 12. Part 2 is formed. On the periphery of the imaging unit 2, a light shielding unit 3 including a light shielding color filter 5 formed by photocuring the photosensitive resin composition of the present invention is formed.

  In FIG. 1, a photoelectric conversion element 12, such as a CCD or CMOS, transfer electrodes 14a and 14b, a planarization layer 18a, and the like necessary for the solid-state imaging device 1 can be formed according to a known IC manufacturing method. The color filters (4R, 4G, 4B) and the light-shielding color filter 5 can be formed by a photoresist technique. The planarizing layer 18b may also be formed on the color filters (4R, 4G, 4B). Furthermore, it is preferable to provide a microlens 17 on the color filters (4R, 4G, 4B) for condensing light.

A photosensitive resin composition containing titanium black as a visible light and infrared light shielding agent is uniformly applied on the silicon substrate 10 on which the color filter (4R, 4G, 4B) is formed, heated, and dried. A film is formed. Subsequently, a commercially available i-line is passed through a mask in which a mask pattern is formed in the dry coating film so as to open the imaging unit 2 and cover a photoelectric conversion element or the like used for dark current measurement. The pattern of the light-shielding color filter 5 can be obtained by exposure with a stepper or the like, alkali development, washing with water and drying.
Furthermore, after the planarization layer 18b and the microlens 17 are formed on the obtained substrate as necessary, dicing and packaging are performed to obtain the solid-state imaging device 1.
At this time, the film thickness of the optical functional layer from the silicon substrate surface to the lower surface of the microlens is preferably 5 μm or less, more preferably 4.5 μm or less, and particularly preferably 4 μm or less.

In the solid-state imaging device of the present invention, in addition to disposing a light-shielding color filter on the periphery of the imaging unit on the front surface side as described above, a light-shielding filter can also be disposed on the back surface facing the surface with the imaging unit. preferable.
Specifically, in the solid-state imaging device having a plurality of protruding electrodes for connecting to the wiring substrate on the back surface of the solid-state imaging device, it is preferable to provide a light-shielding color filter in a region other than the protruding electrodes on the back surface.

  Conventionally, in a solid-state imaging device having a protruding electrode on the back surface, stray light enters the solid-state imaging device from between the solid-state imaging device and the solid-state imaging device wiring board, and the captured image tends to deteriorate due to generation of dark current. is there. The solid-state imaging device of the present invention can prevent the stray light from entering by providing a light-shielding color filter on the back surface. Therefore, even if the conventional injection of the light-shielding underfill resin for preventing the intrusion of stray light is omitted, the generation of dark current due to the stray light from the back side can be suppressed and the color reproducibility can be improved. it can.

  A preferred embodiment of the solid-state imaging device of the present invention will be described with reference to FIGS. FIG. 2 is a block diagram showing an example of the solid-state imaging device of the present invention. FIG. 3 is a cross-sectional view taken along the line A-A ′ in FIG. 2.

As illustrated in FIG. 2, the solid-state imaging device 20 includes a solid-state imaging device 24 having an imaging unit 2, a light shielding unit 3, and a bonding pad 30.
FIG. 3 is a cross-sectional view of the solid-state imaging device 20 including the solid-state imaging device 24 and the wiring board 21 shown in FIG. The solid-state imaging device 24 includes an imaging unit 2 and a light shielding unit 3 on the front surface, and further includes a light shielding color filter 23 and a protruding electrode 26 on the back surface. Furthermore, an underfill resin 25 may be provided between the solid-state imaging device 24 and the wiring board 21 for the purpose of improving durability and preventing stray light.

A through electrode 27 is formed under the bonding pad 30 formed on the solid-state image sensor 24, and is connected to the protruding electrode 26 provided on the back surface of the solid-state image sensor 24.
The solid-state imaging device 24 can be connected to the wiring board 21 via a plurality of protruding electrodes 26 formed. As the protruding electrode 26, a known one can be used and is not limited. Examples thereof include a solder ball, a gold stud bump, and a gold plating bump.

  When the light-shielding color filter 23 is disposed on the back surface of the solid-state imaging device 24 of the present invention, dark current generated when the imaging light enters the solid-state imaging device as stray light can be reduced.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example. Unless otherwise specified, “part” and “percentage (%)” are based on weight.

(1) Preparation of titanium black dispersion <Preparation of titanium black crude dispersion>
A titanium black crude dispersion was prepared by subjecting the following composition to a high viscosity dispersion treatment using two rolls. The viscosity of the obtained titanium black crude dispersion was 40,000 mPa · s.
In addition, you may knead | mix for 30 minutes with a kneader before a high-viscosity dispersion process.

<Titanium black crude dispersion composition>
Gemco Titanium Black 13M-T: 40 parts Propylene glycol monomethyl acetate (PGMEA) solution of benzyl methacrylate / methacrylic acid copolymer (BzMA / MAA = 70/30 (molar ratio), Mw: 30,000, solid 40% by weight): 6 parts Solsperse 5000 (manufactured by Zeneca): 1 part

  The following component (A) was added to the obtained titanium black crude dispersion, and the mixture was stirred for 3 hours using a homogenizer at 3,000 rpm. The obtained mixed solution was subjected to a dispersion treatment for 4 hours with a disperser using 0.3 mm zirconia beads (manufactured by Dispermat GETZMANN) to obtain a titanium black dispersion. The viscosity of this dispersion was 8.0 mPa · s.

<Component (A)>
Propylene glycol monomethyl acetate solution of benzyl methacrylate / methacrylic acid copolymer (BzMA / MAA = 70/30 (molar ratio), Mw: 30,000, solid content 40% by weight): 10 parts Propylene glycol monomethyl ether acetate (PGMEA) : 140 copies

(2) Preparation of light-sensitive color filter forming photosensitive resin composition Methacrylate / methacrylic acid copolymer (J-1): 6.1 parts Dipentaerythritol hexaacrylate (T-1): 4.8 parts Ethoxylation Pentaerythritol tetraacrylate (T-2): 1.7 parts Titanium black dispersion: 67 parts Propylene glycol monomethyl ether acetate (PGMEA): 15.7 parts Oxime-based initiator ((K-1) below): 7 copies

(Comparative Example 1)
The photosensitive resin composition obtained by the preparation of the above (2) photosensitive resin composition for forming a light-shielding color filter was used as the photosensitive resin composition of Comparative Example 1.

Example 1
A photosensitive resin composition of Example 1 was prepared in the same manner as Comparative Example 1 except that a distilled and dehydrated organic solvent (PGMEA) was used.

(Example 2)
Dissolved components other than titanium black dispersion using distilled dehydrated organic solvent (PGMEA), added molecular sieves 4A thereto, allowed to stand for 3 hours, filtered, and separately prepared titanium black dispersion. A photosensitive resin composition of Example 2 was prepared in the same manner as in Comparative Example 1 except that was prepared.

(Example 3)
Components other than the titanium black dispersion were dissolved using a distilled and dehydrated organic solvent (PGMEA), and molecular sieves 4A was added thereto, allowed to stand for 3 hours, and then filtered. A photosensitive resin composition of Example 3 was prepared in the same manner as in Comparative Example 1 except that a titanium black dispersion that had been filtered and dehydrated using a filter packed with molecular sieves 4A was added thereto.

Example 4
A photosensitive resin composition of Example 4 was prepared in the same manner as in Example 2 except that (K-2) was used instead of the photopolymerization initiator (K-1).

(3) Moisture content measurement method The moisture content of the obtained photosensitive resin compositions of Examples 1 to 4 and Comparative Example 1 was measured by the Karl Fischer method. The results are shown in Table 1.

(4) Adhesive evaluation The obtained photosensitive resin composition was apply | coated to the silicon wafer by the spin coat method, and it heated at 120 degreeC on the hotplate for 2 minutes after that.
Then exposing a pattern of 3mm square from dose 100 mJ / cm ² at an i-line stepper at a 100 mJ / cm ² steps until 1,000 mJ / cm ^2.
After irradiation, paddle development was performed at 23 ° C. for 60 seconds using a tetramethylammonium hydroxide 0.3% aqueous solution (CD-2060 manufactured by FFEM). Thereafter, it was rinsed and washed with a spin shower. The film thickness of the obtained light-shielding color filter was 1.0 μm. The obtained pattern was observed with an optical microscope and a length measurement SEM, and the adhesion was evaluated.
The adhesion failure means that the pattern itself is peeled off or a part of the pattern has peeling or chipping. That is, the irradiation amount with which good adhesion is confirmed refers to an exposure amount (irradiation amount) at which no pattern peeling or chipping has occurred at that exposure amount.

(5) Evaluation of the number of coating defects The obtained photosensitive resin composition was applied to an 8-inch silicon wafer by a spin coating method, and then heated at 120 ° C. for 2 minutes on a hot plate. The film thickness after heating was 1.0 μm.
The number of defects of the substrate was measured with ComPlus manufactured by Applied Materials. The smaller the number of defects, the better.

It is sectional drawing which shows an example of the imaging part of the solid-state image sensor of this invention, and the light-shielding part arrange | positioned at the periphery. It is a schematic plan view which shows an example of the solid-state imaging device provided with the solid-state imaging element of this invention. It is sectional drawing of an example of the solid-state imaging device provided with the solid-state image sensor of this invention.

Explanation of symbols

1: solid-state imaging device 2: imaging unit 3: light shielding unit 4R, 4G, 4B: color filter 5: light shielding color filter 10: silicon substrate 12: photoelectric conversion element (light receiving sensor unit)
14a, 14b: Transfer electrode 16: Insulating film 17: Microlens 18a, 18b: Flattening layer 20: Solid-state imaging device 21: Wiring substrate 22: Solid-state imaging chip 23: Light-shielding color filter 24: Solid-state imaging device 25: Underfill Resin 26: Projection electrode 27: Through electrode 30: Bonding pad 50: Solder ball

Claims (8)

(A) Titanium black,
(B) a polymerizable compound,
(C) resin,
(D) a photopolymerization initiator, and
(E) A photosensitive resin composition containing at least an organic solvent,
The water content in the photosensitive resin composition is 3% by weight or less,
Photosensitive resin composition.   The photosensitive resin composition according to claim 1, wherein the moisture content is 2% by weight or less.   The photosensitive resin composition according to claim 1, wherein the moisture content is 1% by weight or less.   The photosensitive resin composition of any one of Claims 1 thru | or 3 containing an oxime type compound as said (D) photoinitiator.   The photosensitive resin composition of any one of Claims 1 thru | or 4 which is an object for solid-state image sensors.   A light-shielding color filter comprising a pattern formed using the photosensitive resin composition according to claim 1. Applying the photosensitive resin composition according to any one of claims 1 to 5 to a substrate;
An image exposure step; and
A process for producing a light-shielding color filter, comprising a step of developing and patterning.   A solid-state imaging device comprising the light-shielding color filter according to claim 6 or the light-shielding color filter obtained by the production method according to claim 7.

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