KR20090103717A - Photosensitive resin composition, light-shielding color filter and production process therefor, and image sensor - Google Patents

Abstract

PURPOSE: A photosensitive resin composition is provided to prepare a light blocking color filter with excellent uniformity of coated film thickness on a wafer. CONSTITUTION: A photosensitive resin composition includes titanium black, two kinds of polymerizable compound, resin, photopolymerization initiator and organic solvent. The light blocking color filter has pattern formed by the photosensitive resin composition. A method for manufacturing the light blocking color filter comprises the steps of: applying the photosensitive resin composition on a substrate; exposing with image; and patterning it by development.

Description

Photosensitive resin composition, light-shielding color filter, its manufacturing method, and solid-state image sensor {PHOTOSENSITIVE RESIN COMPOSITION, LIGHT-SHIELDING COLOR FILTER AND PRODUCTION PROCESS THEREFOR, AND IMAGE SENSOR}

The present invention relates to a photosensitive resin composition, a light-shielding color filter, a manufacturing method thereof, and a solid-state imaging device.

The color filter used for a liquid crystal display device is equipped with the light shielding film called a black matrix for the purpose of shielding the 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) generation due to stray light, improving the image quality, and the like.

As a composition for forming the black matrix for liquid crystal display devices and the light shielding film for solid-state image sensors, the photosensitive resin composition containing black color materials, such as carbon black and titanium black, is known (for example, Unexamined-Japanese-Patent No. 10-A). 246955, Japanese Patent Laid-Open No. 9-54431, Japanese Patent Laid-Open No. 10-46042, Japanese Patent Laid-Open No. 2006-36750, and Japanese Patent Laid-Open No. 2007-115921.

As a black matrix for liquid crystal display devices, a light shielding film for a solid-state image sensor (hereinafter, synonymous with a "light shielding color filter") is mainly required for light shielding in the visible region in addition to the light shielding in the visible region. It is also necessary to provide the light shielding property in an infrared region.

Further, miniaturization is required for the black matrix for liquid crystal display devices, while for light shielding films for solid-state imaging devices, the ability to uniformly light-shield the entire surface of the wafer is required. As a light shielding film for a solid-state image sensor, the light shielding film arrange | positioned at the periphery of the imaging part which is a peripheral edge area of an imaging part (effective pixel area), and / or the light shielding film arrange | positioned between protrusion electrodes in the back surface opposite to the formed surface of the imaging part is important. .

However, using the above-mentioned well-known photosensitive resin composition as a light shielding film for a solid-state image sensor, and forming a light shielding film in the pattern which has an in-plane difference, the film thickness of a light shielding film tends to become thinner than a wafer center part in a wafer peripheral part, and a wafer peripheral part In some cases, the light shielding ability of the device may be lowered.

Moreover, there exists a problem that the light shielding ability becomes low as a result of the adhesiveness of a board | substrate and a light shielding film being inadequate, and a flaw or peeling of a light shielding film generate | occur | producing. The present invention has been made in view of the above problems.

An object of the present invention is to provide a photosensitive resin composition that provides a light-shielding color filter that is excellent in adhesion to a substrate and excellent in uniformity of a coating film thickness on a wafer. Moreover, an object of this invention is to provide the light-shielding color filter formed with the said photosensitive resin composition, its manufacturing method, and a solid-state image sensor.

The said subject of this invention was solved by the means as described in the following <1> and <10>-<12>. It describes below with <2>-<9> which is preferable embodiment.

<1> Photosensitive resin composition containing (A) titanium black, (B) 2 or more types of polymeric compounds, (C) resin, (D) photoinitiator, and (E) organic solvent at least

<2> Photosensitive resin composition as described in said <1> containing 2 or more types of polymeric compounds which have a different number of ethylenically unsaturated groups in 1 molecule as (B) 2 or more types of polymeric compounds,

<3> The photosensitive resin composition as described in said <1> or <2> containing (B) 2 or more types of polymeric compounds containing the complete (meth) acrylic acid ester of 2 or more types of aliphatic polyol which has a different number of hydroxyl groups,

<4> Photosensitive resin composition as described in any one of said <1> to <3> containing (meth) acrylic acid ester of pentaerythritol and / or dipentaerythritol as 2 or more types of polymeric compounds,

<5> Photosensitive resin composition in any one of said <1> to <4> containing an oxime initiator as a photoinitiator (D),

<6> Photosensitive resin composition in any one of said <1> to <5> in which the said oxime initiator is represented by following formula (1),

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

<7> Photosensitive resin composition in any one of said <1> to <6> by which the said oxime initiator is represented by following formula (2),

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

<8> Photosensitive resin composition in any one of said <1> to <7> in which the said oxime initiator is represented by following formula (3),

[In Formula (3), R and X respectively independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, n is an integer of 0-5.]

<9> Photosensitive resin composition in any one of said <1>-<8> which is for solid-state image sensors,

<10> Light-shielding color filter which has pattern formed using photosensitive resin composition in any one of said <1>-<9>,

<11> The light-shielding color characterized by including the process of apply | coating the photosensitive resin composition in any one of said <1> to <9> to a board | substrate, the image exposure process, and the process of developing and patterning. Manufacturing method of filter,

<12> The solid-state image sensor which has the light-shielding color filter as described in <10>.

(Effects of the Invention)

According to this invention, the photosensitive resin composition which can form the light-shielding color filter excellent in adhesiveness with a board | substrate and excellent in coating film thickness uniformity was able to be provided. Moreover, according to this invention, the light-shielding color filter formed using the said photosensitive resin composition, its manufacturing method, and the solid-state image sensor could be provided.

BRIEF DESCRIPTION OF THE DRAWINGS 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 circumferential edge.

2 is a schematic plan view showing an example of a solid-state imaging device including the solid-state imaging device of the present invention.

3 is a cross-sectional view of an example of a solid-state imaging device including the solid-state imaging device of the present invention.

(Explanation of symbols for the main parts of the drawing)

1: solid-state imaging element 2: imaging unit

3: shading part 4R, 4G, 4B: color filter

5: light blocking color filter 10: silicon substrate

12: photoelectric conversion element (light receiving sensor) 14a, 14b: transmission electrode

16: insulating film 17: microlens

18a, 18b: planarization layer 20: solid-state imaging device

21: wiring board 22: solid-state imaging chip

23: light blocking color filter 24: solid-state image sensor

25: underfill resin 26: projection electrode

27: through electrode 30: bonding pad

50: solder ball

(1) photosensitive resin composition

The photosensitive resin composition of this invention contains at least (A) titanium black, (B) 2 or more types of polymeric compounds, (C) resin, (D) photoinitiator, and (E) organic solvent. The photosensitive resin composition of this invention may contain another component as an additive in addition to said (A)-(E).

Moreover, the photosensitive resin composition of this invention can be used suitably as a photosensitive resin composition for solid-state image sensors, and can be used suitably in order to form a light shielding color filter (light shielding film) in a solid-state image sensor.

Hereinafter, each component of the photosensitive resin composition of this invention is demonstrated.

(A) titanium black

The photosensitive resin composition of this invention contains titanium black as a black color material.

Titanium black has a higher light shielding ability in the infrared light region than conventional pigments and dyes dispersed and dissolved in a photosensitive resin composition, particularly a photosensitive resin composition for color filters, and therefore, an infrared light region that cannot be shielded by overlapping color filters. Can be reliably shielded. In particular, the light shielding film which hardened the photosensitive resin composition of this invention has the high light shielding property of an infrared light region, and can suppress the noise by the dark current of the solid-state image sensor provided with this.

In addition, since titanium black has a smaller absorption of the i-line irradiated for pattern formation as compared with carbon black generally used as a black color material, titanium black can be cured with a small exposure amount and contribute to improvement in productivity.

Titanium black is a black particle having a titanium atom. Preferably, it is low titanium oxide, titanium oxynitride, etc. Titanium black particles can chemically modify the surface as necessary for the purpose of improving dispersibility and suppressing cohesiveness. Specifically, it is possible to coat the surface of titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and also by water repellent material as shown in Japanese Patent Laid-Open No. 2007-302836. Surface treatment is also possible.

In addition, the titanium black is one or two of black pigments such as complex oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, and aniline black for the purpose of adjusting dispersibility, colorability, and the like. You may contain it in combination of species or more.

It is also possible to add pigments such as existing red, blue, green, yellow, cyan, magenta, violet, orange, or dyes for the purpose of controlling the light shielding properties of the desired wavelengths.

Examples of commercially available products of the titanium black are JEMCO Inc. Products (Sold by Mitsubishi Materials Corporation) Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, Ako Kasei CO., LTD. The product Tilack D etc. can be mentioned.

As a method of producing the titanium black, a method of reducing a mixture of titanium dioxide and metal titanium by heating in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine dioxide obtained by high temperature hydrolysis of titanium tetrachloride Method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), Method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, Japan Japanese Patent Application Laid-Open No. 61-201610), and a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide to reduce the temperature at high temperature in the presence of ammonia (Japanese Patent Publication No. 61-201610), but are limited thereto. It doesn't happen.

Although there is no restriction | limiting in particular in the particle diameter of the particle | grains of the said titanium black, From an viewpoint of dispersibility, coloring property, and the influence on the yield in a solid-state image sensor, average particle diameter (average primary particle diameter) is 10- It is preferable that it is 150 nm, It is more preferable that it is 10-100 nm, 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.

Although the specific surface area of the said titanium black is not specifically limited, It is preferable that the value measured by the BET method is about 5-150 m <2> / g in order for the water repellency after surface treatment of titanium black to a predetermined | prescribed performance to become a predetermined performance. It is more preferable that it is about 20-100 m <2> / g.

In this invention, titanium black and another black color material may be used together, black color materials other than titanium black may be used individually by 1 type, or may use 2 or more types together.

Although various well-known black pigments and black dyes can be used as a black color material which can be used together, carbon black, iron oxide, manganese oxide, graphite, etc. are preferable especially from a viewpoint which can implement | achieve a high optical density in a small quantity, and especially, Carbon black is preferred.

The said carbon black is black microparticles | fine-particles containing the microparticles | fine-particles of carbon, and a preferable particle | grain is what contains the microparticles | fine-particles of the carbon of about 3-1,000 nm in diameter. Further, the surface of the fine particles may have a functional group containing various carbon atoms, hydrogen atoms, oxygen atoms, sulfur atoms, nitrogen atoms, halogens, inorganic atoms and the like.

Moreover, carbon black can change a characteristic by changing particle diameter (particle size), a structure (particle connection), and a surface property (functional group) variously according to the intended use. It is also possible to change affinity with blackness and resin or to impart conductivity.

Specific examples of the carbon black include, for example, carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, and MCF88 manufactured by Mitsubishi Chemical Corporation. , # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond black I, diamond black LI, diamond black II, diamond black N339, diamond black SH, diamond black SHA, diamond black LH, diamond black H, diamond black HA, diamond black SF, diamond black N550M, diamond black E, diamond black G, diamond black R, diamond black N760M, diamond black LP; Carbon Black Thermomax N990, N991, N907, N908, N990, N991, N908 from Cancarb; Asahi Carbon Co., Ltd. Products: 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; Carbon Black Color Black Fw200, Color Black Fw2, Color Black Fw2V, Color Black Fw1, Color Black Fw18, Color Black S170, Color Black S160, SPECIAL BLACK 6, SPECIAL BLACK 5, SPECIAL BLACK 4, SPECIAL BLACK 4A, Printex U , Printex V, Printex 140U, Printex 140V, and the like.

In addition, it may be preferable that the said carbon black has insulation.

Carbon black having insulation is carbon black showing insulation when the volume resistance as a powder is measured by the following method. This insulation is based on having an organic compound on the surface of the carbon black particles, for example, by adsorbing, coating or chemically bonding (grafting) the organic material on the surface of the carbon black particles.

That is, carbon black is dispersed in propylene glycol monomethyl ether acetate so that benzyl methacrylate and methacrylic acid are in a molar ratio of 70:30 copolymer (weight average molecular weight 30,000) and 20:80 weight ratio to prepare a coating solution, and the thickness thereof. It is applied to a chromium substrate of 1.1 mm and 10 cm x 10 cm to produce a coating film having a dry film thickness of 3 μm, and the coating film is subjected to heat treatment at 220 ° C. for about 5 minutes in a hot plate, followed by JISK6911. It is applied with a high resistivity meter Hiresta UP (MCP-HT450) manufactured by Mitsubishi Chemical Corporation, and the volume resistance value is measured under an environment of 65% relative humidity at 23 ° C. And as this volume resistance value, carbon black which shows 10 ⁵ ohm * cm or more, More preferably, 10 ⁶ ohm * cm or more, Especially preferably, 10 ⁷ ohm * cm or more is preferable.

As carbon black as mentioned above, Unexamined-Japanese-Patent No. 11-60988, Unexamined-Japanese-Patent No. 11-60989, Unexamined-Japanese-Patent No. 10-330643, Unexamined-Japanese-Patent No. 11-80583, for example And the resin-coated carbon black disclosed in Japanese Patent Laid-Open No. 11-80584, Japanese Patent Laid-Open No. 9-124969, and Japanese Patent Laid-Open No. 9-95625 can be used.

The average particle diameter (average primary particle diameter) of the black color material used together with titanium black is that the average primary particle diameter is small from the viewpoint of foreign matter generation and the influence on its yield in the manufacture of a solid-state imaging device. desirable. 10-100 nm is preferable, as for an average primary particle diameter, 50 nm or less is more preferable, and 30 nm or less is preferable.

An average particle diameter can be measured by apply | coating a black color material to a suitable board | substrate, and observing with a scanning electron microscope.

Although content of the titanium black in the photosensitive resin composition is not specifically limited, It is preferable that the average transmittance in the visible region-infrared region (400-1,600 nm) of the light-shielding color filter formed becomes 1% or less. It is preferable that an optical density of 2.0 or more is obtained at a film thickness almost equal to color separation filters such as RGB. 10-60 weight% is preferable and, as for the compounding quantity of the titanium black in solid content of the photosensitive resin composition, 20-40 weight% is more preferable.

In the case of using titanium black and another black color material in combination, the preferred weight ratio is 95: 5 to 60:40, more preferably 95: 5 to 70:30, still more preferably 90% of titanium black: other black color material. From 10 to 80:20. Moreover, when there are multiple black color materials to use together, it is preferable to make those total weight into the said range.

By carrying out the weight ratio of titanium black and another black color material in the said range, since the dispersibility in the photosensitive resin composition becomes favorable and the stable coating film without a spot can be formed, it is preferable.

In addition, a dispersing agent having an acid value and an amine number can be used for the dispersion of the titanium black and the carbon black, and specifically, Apercia's Solsper 24000, Solsper's 33500, and BYK-Chemie Japan's Disper BYK 161 can be used. Here, "having an acid value and an amine value" means the case where it has group which has an acid value, when it has group which has an amine value, or when it has both.

As the other dispersant, a homopolymer or a copolymer obtained by polymerizing monomers such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide or derivatives thereof, styrene or derivatives thereof can be used.

As said monomer, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, (alpha) -methylstyrene, p-methoxy styrene, p-tert- butyl styrene, p-phenyl styrene, o-chloro styrene, 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-ethylhexyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, methacrylic acid, methacrylic Methyl acid, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, benzyl methacrylate, 2-ethyl methacrylate (Meth) acrylic acid monomers such as hexyl, stearyl methacrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; Various monomers, such as ethylene, propylene, butylene, vinyl chloride, vinyl acetate, an acrylonitrile, acrylamide, methacrylamide, and N-vinylpyrrolidone, can be illustrated.

As a homopolymer or a copolymer, the homopolymer or copolymer of the above-mentioned monomer can be illustrated. Among these, a (meth) acrylic acid ester polymer is preferable.

Moreover, as a material which can be used for dispersion other than that, resin, such as a polyurethane and a polyimide, and the siloxane-type polymer of Unexamined-Japanese-Patent No. 2002-241616 and 2002-234995 can also be used.

The resin used as the dispersant is not limited in molecular weight as long as it can secure dispersibility, 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 1,000 to 30,000. to be.

As a dispersion medium which disperses black color materials, such as said titanium black and carbon black, as long as it can function as a dispersion solvent, various water-soluble or non-aqueous things can be used, For example, methyl alcohol, ethyl alcohol, isopropyl Alcohols such as alcohol, butyl alcohol and allyl alcohol; Ethylene glycol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol, polyethylene glycol, polypropylene glycol, diethylene glycol monoethyl ether, polypropylene glycol monoethyl ether, polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether, etc. Glycols or derivatives thereof; Glycerol or derivatives thereof such as glycerol, glycerol monoethyl ether and glycerol monoallyl ether; Ethers such as tetrahydrofuran and dioxane; Ketones such as methyl ethyl ketone and methyl isobutyl ketone;

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

When preparing the dispersion liquid of the black color material containing titanium black in this invention, 5-100 weight part of polymer components are added with respect to 100 weight part of black color materials, Preferably 10-100 weight part is added.

If the polymer component is 5 parts by weight or more, the surface properties of the black color material can be maintained better. If the polymer component is 200 parts by weight or less, the characteristics of the originally required black color material such as light shielding properties or coloring properties are further improved. You can.

Known coloring agents, such as pigments or dyes, such as red, blue, green, yellow, cyan, magenta, violet, orange, for the purpose of controlling the light-shielding property of a desired wavelength in addition to the above-mentioned black color material in the photosensitive resin composition of this invention. It is also possible to add.

(B) polymerizable compound

The photosensitive resin composition of this invention contains a polymeric compound. It is preferable that this polymeric compound is a compound which addition-polymerizes by the action | action of a photoinitiator. It is preferable to use the ethylenically unsaturated compound which has at least 1 ethylenically unsaturated bond in a molecule | numerator as said polymeric compound.

As a polymeric compound, the polyfunctional ethylenically unsaturated compound which has two or more terminal ethylenically unsaturated bonds is more preferable. Such compound groups are well known in the above industrial field, and in the present invention, these can be used without particular limitation. These have, for example, chemical forms such as monomers, dimers, trimers and oligomers, or mixtures thereof. It is preferable that molecular weight is 70-2,000, and, as for a polymeric compound, it is more preferable that it is 100-1,000.

Examples of the monomer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and preferably unsaturated carboxyl Esters of acids and aliphatic polyhydric alcohol compounds and amides of unsaturated carboxylic acids and aliphatic polyamine compounds are used. Furthermore, addition reaction products of unsaturated carboxylic esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and mercapto groups with monofunctional or polyfunctional isocyanates or epoxys, and monofunctional or polyfunctional carboxyl groups Acid dehydration condensation reactants are also preferably used. Moreover, the addition reaction product of unsaturated carboxylic acid ester or amides which have electrophilic substituents, such as an isocyanate group and an epoxy group, and monofunctional or polyfunctional alcohol, amines, and thiols, and also detachable substituents, such as a halogen group and a tosyloxy group, Substituted reactants of unsaturated carboxylic acid esters or amides having monofunctional or polyfunctional alcohols, amines and thiols are also preferable. As another example, it is also possible to use a compound group substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the above unsaturated carboxylic acid.

Specific examples of monomers of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, and propylene. Glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylol ethane triacrylate, hexanediol diacrylate, 1,4-cyclo Hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, Sorbbi Tol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid EO modified triacrylate, and the like.

As methacrylic acid ester, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol ethane trimethacrylate, ethylene glycol dimethacryl Laterate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipenta Erythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- (methacryloxy Ethoxy) phenyl] dimethylmethane and the like.

As the itaconic acid ester, ethylene glycol dietaconate, propylene glycol dietaconate, 1,3-butanediol dietaconate, 1,4-butanediol dietaconate, tetramethylene glycol dietaconate, pentaerythritol dietaconate, sorbitol tetratacoate Nate and the like.

Examples of the crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramalate and the like.

As examples of other esters, for example, aliphatic alcohol esters described in JP-A-51-47334, JP-A-57-196231, JP-A-59-5240, and JP-A-JP The thing which has the aromatic skeleton of Unexamined-Japanese-Patent No. 59-5241, Unexamined-Japanese-Patent No. 2-226149, the thing containing the amino group of Unexamined-Japanese-Patent No. 1-165613, etc. are also used preferably. In addition, the above-mentioned ester monomer can be used also as a mixture.

Moreover, as an example of the monomer of the amide of an aliphatic polyhydric amine compound and an unsaturated carboxylic acid, methylenebis- acrylamide, methylenebis-methacrylamide, 1, 6- hexamethylenebis- acrylamide, 1, 6- hexamethylene bis- Methacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like.

As an example of another preferable amide monomer, what has a cyclohexylene structure of Unexamined-Japanese-Patent No. 54-21726 is mentioned.

Moreover, the urethane type addition polymeric compound manufactured using addition reaction of an isocyanate and a hydroxyl group is also preferable, As such a specific example, 2 or more isocyanate groups per molecule are described, for example in Unexamined-Japanese-Patent No. 48-41708. The vinylurethane compound etc. which contain two or more polymerizable vinyl groups in 1 molecule which added the vinyl monomer containing the hydroxyl group represented by following formula (A) to the polyisocyanate compound which have is mentioned.

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. ]

Furthermore, urethane acrylates and Japanese Patent Publication Nos. 58-49860, Japan, such as those described in Japanese Patent Laid-Open Nos. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. Hei 2-16765. Also preferred are urethane compounds having an ethylene oxide-based skeleton described in each of Japanese Patent Application Laid-Open No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. In addition, addition polymerizable compounds having an amino structure or a sulfide structure in the molecules described in each of JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. By doing so, the photosensitive resin composition excellent in the photosensitive speed can be obtained.

As other examples, polyester acrylates, epoxy resins, and (meth) as described in Japanese Patent Application Publication No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490 Polyfunctional acrylates and methacrylates, such as epoxy acrylate which made acrylic acid react, are mentioned. In addition, Japanese Unexamined Patent Publication No. 46-43946, Japanese Patent Publication No. 1-40337, Japanese Patent Publication No. 1-40336, the specific unsaturated compound of each publication, and the vinyl force of Japanese Patent Publication No. 2-25493 Phonic acid compounds and the like. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. In addition, Japan Adhesion Society Vol. 20, No. It is also possible to use those introduced as photocurable monomers and oligomers on pages 7,300 to 308 (1984).

About these polymeric compounds, the detail 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 selects from the following viewpoints.

From the viewpoint of sensitivity, a structure having a high content of unsaturated groups per molecule is preferable, and in most cases, bifunctional or more is preferable. Moreover, in order to make the intensity | strength of a cured film high, a trifunctional or more thing is good, and also the sensitivity by using together the thing of another functional water and another polymerizable group (for example, acrylic ester, methacrylic ester, a styrene type compound, a vinyl ether type compound) is used. The method of adjusting both and strength is also effective.

Moreover, also about compatibility and dispersibility with other components (for example, photoinitiator, titanium black, etc. resin) contained in the photosensitive resin composition, selection and use method of a polymeric compound are important factors, for example, low purity The compatibility can be improved by using a compound and using 2 or more types together. Moreover, a specific structure can also be selected in order to improve adhesiveness with hard surfaces, such as a board | substrate.

Although there is no limitation in particular as content (2 or more types of total content) of the polymeric compound in the total solid of the photosensitive resin composition of this invention, From a viewpoint of obtaining the effect of this invention more effectively, 10 to 80 weight% is preferable, 15-75 weight% is more preferable, and 20-60 weight% is especially preferable.

In this invention, 2 or more types of polymeric compounds are used together. Moreover, you may use together 3 or more types of polymeric compounds. As 2 or more types of polymeric compounds, it is preferable to use together 2 or more types of ethylenically unsaturated compounds in which the number (functional water) of the ethylenically unsaturated groups which exist in 1 molecule differs.

Although the weight ratio of the polymeric compound used together is not specifically limited, When using 2 types of polymeric compounds, it is preferable that it is 95: 5-5: 95, It is more preferable that it is 80: 20-20: 80, It is more preferable that it is 70: 30-30: 70. In addition, when using 3 or more types of polymeric compounds together, it is preferable that the weight ratio of arbitrary 2 types of polymeric compounds is in the said range.

Moreover, it is preferable that a polymeric compound is a complete (meth) acrylic acid ester of the aliphatic polyol which has a hydroxyl group in a molecule | numerator. It is more preferred that the polymerizable compound is a fully acrylic acid ester of a fatty acid polyol having a hydroxyl group in the molecule.

Examples of fully (meth) acrylic acid esters of bifunctional aliphatic polyols include ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth). ) Acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, and average molecular weight The polyethyleneglycol di (meth) acrylate which is the range of this 200-2,000 can be illustrated.

As a complete (meth) acrylic acid ester of a trifunctional aliphatic polyol, trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, the alkylene oxide modified tri (meth) acrylate of trimethylolpropane, and trimethylol Propane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, and tri ((meth) acryloyloxyethyl) isocyanurate can be illustrated.

As a fully (meth) acrylic acid ester of a tetrafunctional aliphatic polyol, it is a pentaerythritol tetra (meth) acrylate, and as a fully (meth) acrylic acid ester of a 6 functional aliphatic polyol, a dipentaerythritol hexa (meth) acrylate, sorbitol hexaacrylate, As a fully (meth) acrylic acid ester of an 8-functional aliphatic polyol, tripentaerythritol octa (meth) acrylate can be illustrated, respectively.

In this invention, it is more preferable to use together the ethylenically unsaturated compound of the other functional water selected from 2-6 functional, and it is 2 types from the 4-6 functional (meth) acrylic acid ester which is a complete (meth) acrylic acid ester of an aliphatic polyol. It is more preferable to use together.

Among these, it is preferable to contain the (meth) acrylic acid ester of pentaerythritol and / or dipentaerythritol, and it is more preferable to contain the (meth) acrylic acid ester of pentaerythritol and dipentaerythritol. As an especially preferable form, the form containing the full (meth) acrylic acid ester of pentaerythritol and the full (meth) acrylic acid ester of dipentaerythritol can be illustrated, and also containing pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate. The form can be illustrated.

(C) resin

The photosensitive resin composition of this invention contains resin as a binder (film forming agent). It is preferable that this resin is alkali-soluble resin.

It is preferable to use linear organic polymer as said resin. As such a "linear organic polymer", a well-known thing can be used arbitrarily. Preferably, linear organic polymers are selected that are soluble or swellable in water or weakly alkaline water to enable water or weakly alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also as a water, a weak alkaline water or an organic solvent developer. For example, the use of water soluble organic polymers allows water development. As such a linear organic polymer, a radical polymer having a carboxylic acid group in the side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication 54 -25957, Japanese Patent Laid-Open No. 54-92723, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048, each of which is described, that is, a resin in which a monomer having a carboxyl group is singly or copolymerized. And resins obtained by hydrolyzing or half-esterifying or half-amidating an acid anhydride unit alone or copolymerizing monomers having an acid anhydride, epoxy acrylates modified with an unsaturated monocarboxylic acid and an acid anhydride, and the like. . Acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxy styrene etc. are mentioned as a monomer which has a carboxyl group, A maleic anhydride etc. are mentioned as a monomer which has an acid anhydride.

Similarly, there are acidic cellulose derivatives having a carboxylic acid group in the side chain. In addition, what added the cyclic anhydride to the polymer which has a hydroxyl group is useful.

As a resin (for example, alkali-soluble resin) in this invention, when using a copolymer, as a compound to copolymerize, you may use monomers other than the above-listed monomer. As an example of another monomer, the compound of following (1)-(12) is mentioned.

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl meth Acrylic acid esters having aliphatic hydroxyl groups such as acrylate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl methacrylate, and methacrylic acid esters.

(2) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, Aliphatic hydroxyl groups such as 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate Acrylic esters having no.

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Cyclohexyl, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1 Methacrylic acid ester which does not have aliphatic hydroxyl groups, such as propenyl methacrylate, allyl methacrylate, 2-allyloxy ethyl methacrylate, and propargyl methacrylate.

(4) Acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide , N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide, N, N- diallyl acrylamide, N, N- diallyl methacrylamide, allyl acrylamide, Acrylamide or methacrylamide, such as allyl methacrylamide.

(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) Styrene, such as styrene, (alpha) -methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxy styrene.

(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-acryloyl acrylamide, N-acetyl methacrylamide, N-propionyl methacrylamide, and N- (p-chlorobenzoyl) methacrylamide.

(12) Methacrylic acid monomers in which a hetero atom is bonded at the α position. For example, the compound described in Unexamined-Japanese-Patent No. 2002-309057, Unexamined-Japanese-Patent No. 2002-311569, etc. are mentioned.

Among these, (meth) acrylic resins having an allyl group, a vinyl ester group and a carboxyl group in the side chain, and alkali-soluble resins having double bonds in the side chains described in JP-A-2000-187322 and JP-A-2002-62698; Alkali-soluble resin which has an amide group in the side chain described in Unexamined-Japanese-Patent No. 2001-242612 is preferable because it is excellent in the balance of film strength, a sensitivity, and developability.

Japanese Patent Publication No. 7-12004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Publication No. 63-287944, Japanese Patent Publication It has a urethane-based binder polymer containing acid groups described in Japanese Patent Application Laid-Open No. 63-287947 and Japanese Patent Laid-Open No. 1-271741, and an acid group and double bond described in Japanese Patent Application Laid-Open No. 2002-107918. Since the urethane-based binder polymer is very excellent in strength, it is advantageous from the viewpoint of chain resistance and low exposure aptitude.

In addition, an acetal modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Laid-Open No. 2001-318463, and the like is preferable because of its excellent balance between film strength and developability.

In addition, polyvinylpyrrolidone, polyethylene oxide, etc. are useful as water-soluble linear organic polymer. In addition, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane, epichlorohydrin, etc. are also useful in order to raise the strength of a hardened film.

In the present invention, a resin having a monomer unit having a polymerizable group and a monomer unit having an acidic group among the resins described above is preferable. As a monomer unit which has the said polymeric group, the monomer unit which has an ethylenically unsaturated group is preferable, and the monomer unit which has an acryloyloxy group or a methacryloyloxy group in a side chain is more preferable. As a monomer unit which has an acidic group, the monomer unit which has a sulfonic acid group or a carboxyl group is preferable, and the 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 this invention, Preferably it is 5,000 or more, More preferably, it is the range of 10,000-300,000, About a number average molecular weight, Preferably it is larger than 2,000, More preferably It is in the range of 30 to 25 million. As for polydispersity (weight average molecular weight / number average molecular weight), 1 or more is preferable, More preferably, it is the range of 1.1-10.

These resins may be any of random polymers, block polymers and graft polymers.

Resin in this invention can be synthesize | combined by a conventionally well-known method. As a solvent used at the time of synthesis, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy Ethyl acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, lactic acid Methyl, ethyl lactate, dimethyl sulfoxide, water, etc. are mentioned. These solvents are used individually or in mixture of 2 or more types.

As a radical polymerization initiator used when synthesize | combining resin in this invention, well-known compounds, such as an azo initiator and a peroxide initiator, are mentioned.

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

(D) photoinitiator

The photosensitive resin composition of this invention contains a photoinitiator.

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, start efficiency, absorption wavelength, availability, cost, and the like.

The photoinitiator which can be used for this invention is a compound which absorbs actinic radiation (light) and produces | generates a polymerization start species. Examples of the activating radiation include gamma rays, beta rays, electron beams, ultraviolet rays, visible rays, and infrared rays.

As a photoinitiator, For example, the at least 1 active halogen compound chosen from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl substituted coumarin compound, a lophine dimer, a benzophenone compound, an acetophenone compound And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds.

As the halomethyloxadiazole compound, 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound described in JP-A-57-6096, 2-trichloromethyl-5-styryl- 1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxysty Reel) -1,3,4-oxadiazole etc. are mentioned.

As the halomethyl-s-triazine compound, the vinyl-halomethyl-s-triazine compound described in Japanese Patent Publication No. 59-1281 and 2- (naphtho-1-described in Japanese Patent Publication No. 53-133428 (I) -4,6-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-meth Oxystyryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-butoxynaphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- [4- (2-methoxyethyl) naphtho-1-yl]- 4,6-bis (trichloromethyl) -s-triazine,

2- [4- (2-ethoxyethyl) naphtho-1-yl] -4,6-bis (trichloromethyl) -s-triazine, 2- [4- (2-butoxyethyl) naphtho -1-yl] -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methoxynaphtho-1-yl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (6-methoxy-5-methylnaphtho-2-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (6-methoxynaphtho-2- Yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (5-methoxynaphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4,7-dimethoxynaphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (6-ethoxynaphtho-2-yl) -4, 6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxynaphtho-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 (ethoxy Carbonylmethyl) 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-chloroethylamino Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -[pN, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloro Rommethyl) -s-triazine,

4- [pN- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) amino Phenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloro) Rhomethyl) -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) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

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

4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycar Bonylmethylaminophenyl) -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 ( Trichloromethyl) -s-triazine,

4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-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-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, etc. are mentioned.

Other than Midori Kagaku Co., Ltd. TAZ series products (e.g. TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123), T series (e.g., PANCHIM products) T-OMS, T-BMP, TR, TB), IRGACURE series from Ciba Specialty Chemicals (e.g. IRGACURE 651, IRGACURE 184, IRGACURE 500, IRGACURE 1000, IRGACURE 149, IRGACURE 819, IRGACURE 261), DAROCUR series (example For example, DAROCUR 1173), 4,4'-bis (diethylamino) benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1 -(O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 2-benzyl-2-dimethylamino-4-morpholino Butyrophenone, 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-diphenylimida Zolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazole Reel dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer , Benzoin isopropyl ether and the like can also be preferably used.

As a photoinitiator, the compound which does not have a halogen atom is preferable, In addition, the initiator with high sensitivity with respect to i line | wire is preferable, and a lophine dimer and an oxime type compound can be illustrated. As an oxime type compound, an oxime ester type compound is more preferable.

2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (O-acetyloxime) -1- [9-ethyl-6 among oxime system photoinitiators -(2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is preferred.

Moreover, as an oxime system photoinitiator, the compound (henceforth a "specific oxime compound") represented by following formula (1) is also preferable. The specific oxime compound may be an oxime compound of the (E) form or an oxime compound of the (Z) form or a mixture of the (E) and (Z) forms.

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

As a monovalent substituent represented by said R, it is preferable that it is a monovalent nonmetallic atom group.

Examples of the monovalent non-metallic atom group include alkyl group, aryl group, alkenyl group, alkynyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, phosphinoyl group, heterocyclic group, Alkylthiocarbonyl group, an arylthiocarbonyl group, a dialkylaminocarbonyl group, a dialkylaminothiocarbonyl group, etc. are mentioned. In addition, these groups may have one or more substituents. In addition, the substituent mentioned above may be substituted by the other 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 , Alkoxycarbonyl or aryloxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group, acyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryl Arylsulfanyl groups such as acyl groups such as royl group, methacryloyl group and methoxalyl group, alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group, phenylsulfanyl group and p-tolylsulfanyl group, methylamino group and cyclo Dialkylamino groups, such as alkylamino groups, such as a hexylamino group, a dimethylamino group, a diethylamino group, a morpholino group, and a piperidino group, an arylamino group, such as a phenylamino group and p-tolylamino group, Alkyl groups, such as a methyl group, an ethyl group, a tert- butyl group, a dodecyl group, a phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, and aryl groups, such as a phenanthryl group, etc. Wheat, mercapto, sulfo, mesyl, p-toluenesulfonyl, amino, nitro, cyano, trifluoromethyl, trichloromethyl, trimethylsilyl, phosphono, trimethylammonium, dimethylsulfonium, Triphenyl phenacyl phosphonium group etc. are mentioned.

As an alkyl group which may have a substituent, a C1-C30 alkyl group is preferable, Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, an 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-fluoro Penacyl group, 3-trifluoromethyl penacyl group, and 3-nitrophenacyl group are illustrated.

As an aryl group which may have a substituent, a C6-C30 aryl group is preferable, Specifically, a phenyl group, a biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1- Pyrenyl, 5-naphthacenyl, 1-indenyl, 2-azenyl, 9-fluorenyl, terphenyl, quarterphenyl, o-, m- and p-tolyl, xylyl, o-, m- and p-cumenyl group, mesityl group, pentalenyl group, vinaphthalenyl group, ternaphthalenyl group, quarternaphthalenyl group, heptarenyl group, biphenylenyl group, indasenyl group, fluoranthhenyl group, acenaph Thilenyl group, aceanthrylenyl group, penalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group Neyl group, crysenyl group, naphthacenyl group, playadenyl group, pisenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexape Group, a hexahydro hexenyl group, a hexenyl group ruby, nose Ro group, tri tilre naphthyl group, a heptadecyl group, a heptadecyl hexenyl group, a pyran group Trail, Oh and ballet carbonyl group can be exemplified.

As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, and a vinyl group, an allyl group, and a styryl group can be illustrated specifically ,.

As an alkynyl group which may have a substituent, a C2-C10 alkynyl group is preferable, and an ethynyl group, a propynyl group, and a propargyl group can be illustrated specifically ,.

As an alkyl sulfinyl group which may have a substituent, a C1-C20 alkyl sulfinyl group is preferable, Specifically, methyl sulfinyl group, ethyl sulfinyl group, propyl sulfinyl group, isopropyl sulfinyl group, butyl sulfinyl group, hexyl sulfinyl group, and cyclo Hexyl sulfinyl group, octyl sulfinyl group, 2-ethylhexyl sulfinyl group, decanoyl sulfinyl group, dodecanoyl sulfinyl group, octadecanoyl sulfinyl group, cyanomethyl sulfinyl group, and methoxymethyl sulfinyl group can be illustrated.

As an aryl sulfinyl group which may have a substituent, a C6-C30 aryl sulfinyl group is preferable, Specifically, a phenyl sulfinyl group, 1-naphthyl sulfinyl group, 2-naphthyl sulfinyl group, 2-chlorophenyl sulfinyl group, 2 -Methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulphi Neyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfinyl group, and 4-dimethylaminophenyl Sulfinyl groups can be exemplified.

The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specifically, a methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, and cyclo Hexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, and perfluoroalkylsulfonyl Ponyyl groups can be exemplified.

As an arylsulfonyl group which may have a substituent, a C6-C30 arylsulfonyl group is preferable, Specifically, a phenylsulfonyl group, 1-naphthylsulfonyl group, 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-nitrophenylsulfo Neyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, and 4-dimethylaminophenyl Sulfonyl groups can be exemplified.

As an acyl group which may have a substituent, a C2-C20 acyl group is preferable, Specifically, an acetyl group, propanoyl group, butanoyl group, trifluoroacetyl group, pentanoyl group, benzoyl group, 1-naphthoyl group, 2 -Naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2- Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-sia Nobenzoyl group and 4-methoxybenzoyl group can be exemplified.

As an alkoxycarbonyl group which may have a substituent, a C2-C20 alkoxycarbonyl group is preferable, Specifically, a methoxycarbonyl group, an ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, Octadecyloxycarbonyl group and trifluoromethyloxycarbonyl group can be illustrated.

Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, 4 -Dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxy Carbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, and 4-methoxyphenyloxycarbonyl group Can be illustrated.

As a phosphinoyl group which may have a substituent, a C2-C50 phosphinoyl group is preferable, Specifically, a dimethyl phosphinoyl group, diethyl phosphinoyl group, dipropyl phosphinoyl group, diphenyl phosphinoyl group, dimethoxy phospho A pinoyl group, a diethoxy phosphinoyl group, a dibenzoyl phosphinoyl group, and a bis (2, 4, 6-trimethylphenyl) phosphinoyl group can be illustrated.

As a heterocyclic group which may have a substituent, the aromatic or aliphatic heterocycle containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom is preferable.

Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group, kuromeryl group, xanthenyl group, phenoxa Thiynyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolinyl group, isoindolinyl group, 3H-indolyl group , Indolyl group, 1H-indazolyl group, furinyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnaolinyl group, Pterridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenantridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenarsazinyl group, Isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromenyl group, chromanyl group, pyrrolidinyl group, pyrrole Linyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperidyl, piperazinyl, indolinyl, isoindolinyl, quinuclininyl, morpholinyl, And thioxanthryl groups can be exemplified.

Specific examples of the alkylthiocarbonyl group which may have a substituent include methylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, hexylthiocarbonyl group, octylthiocarbonyl group, decylthiocarbonyl group, octadecylthiocarbonyl group, and trifluoromethylthiocarbonyl group. May be exemplified.

Specific examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, and 4-dimethylaminophenyl. Thiocarbonyl 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-cyanophenylthiocarbonyl group, and 4-methoxyphenylthiocarbonyl group. .

Specific examples of the dialkylaminocarbonyl group which may have a substituent include dimethylaminocarbonyl group, diethylaminocarbonyl group, dipropylaminocarbonyl group, and dibutylaminocarbonyl group.

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

Especially, from a viewpoint of high sensitivity, an acyl group is more preferable as R, More specifically, an acetyl group, a propanoyl group, a benzoyl group, and a toluyl group are more preferable.

As a monovalent substituent represented by said B, an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group is represented. In addition, these groups may have one or more substituents. The substituent mentioned above can be illustrated as a substituent. In addition, the substituent mentioned above may be substituted by the other substituent.

Especially, it is the structure shown below preferably.

In the following structure, Y, X, and n are synonymous with Y, X, and n in Formula (2) mentioned later, respectively, and their preferable example is also the same.

As a bivalent organic group represented by said A, a C1-C12 alkylene group, a cyclohexylene group, an alkynylene group is mentioned. In addition, these groups may have one or more substituents. The substituent mentioned above can be illustrated as a substituent. In addition, the substituent mentioned above may be substituted by the other substituent.

Among them, A is an alkylene group substituted with an unsubstituted alkylene group and an alkyl group (for example, methyl group, ethyl group, tert-butyl group and dodecyl group) and alke from the viewpoint of increasing the sensitivity and suppressing coloring due to heating and aging. Alkylene group substituted by the nil 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, Preference is given to alkylene groups substituted with styryl group).

As an aryl group represented by said Ar, a C6-C30 aryl group is preferable and may have a substituent. The substituent mentioned above can be illustrated as a substituent.

Specifically, a phenyl group, a biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azle Neyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, xylyl group, o-, m- and p-cumenyl group, mesityl group, pentalenyl group, vinaphthale Nilyl group, ternaphthalenyl group, quarternaphthalenyl group, heptarenyl group, biphenylenyl group, indasenyl group, fluoranthhenyl group, acenaphthylenyl group, aceanthrylenyl group, penalenyl group, fluorenyl group, anthryl Group, bianthracenyl group, teranthracenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, playadenyl group, pisenyl group, Peryllenyl group, pentaphenyl group, pentaxenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, coronyl group, trinaphthyllenyl group, heptaphenyl group, hep Hexenyl group, a pyran tray group, and o can be ballet carbonyl group is mentioned.

Especially, a substituted or unsubstituted phenyl group is preferable from a viewpoint of raising a sensitivity and suppressing coloring by time-lapse of heating.

In Formula (1), it is preferable from a viewpoint of a sensitivity that the structure of "SAr" formed as S adjacent to said Ar is a structure shown below. In addition, Me represents a methyl group, Et represents an ethyl group.

It is preferable that the specific oxime compound in this invention is a compound represented by following formula (2).

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

R, A, and Ar in Formula (2) are synonymous with R, A, and Ar in said Formula (1), and its preferable example is also the same.

Examples of the monovalent substituent represented by X include alkyl, aryl, alkenyl, alkynyl, alkoxy, aryloxy, acyloxy, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, arylsulfinyl and alkylsulfonyl And an arylsulfonyl group, acyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, amino group, phosphinoyl group, heterocyclic group, and halogen atom. In addition, these groups may have one or more substituents. The substituent mentioned above can be illustrated as a substituent. In addition, the substituent mentioned above may be substituted by the other 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 group in the above X Alkyl group, aryl group, alkenyl group, alkynyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group and phosphinoyl group of R in said Formula (1) And a heterocyclic group are synonymous, and its preferable range is also the same.

As an alkoxy group, a C1-C30 alkoxy group is preferable, Specifically, a methoxy group, an ethoxy group, a propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group, tert- butoxy group, and pentyl octa Period, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, ethoxycarbonylmethyl group, 2-ethylhexyl jade Cycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octyl Aminocarbonylmethyloxy group, N-methyl-N-benzylaminocarbonylmethyloxy group, benzyloxy group, and cyanomethyloxy group can be illustrated.

As an aryloxy group, a C6-C30 aryloxy group is preferable, Specifically, a phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-meth Methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group, 4-fluorophenyl ox The time period, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, and 4-phenylsulfanylphenyloxy group can be illustrated.

As an acyloxy group, a C2-C20 acyloxy group is preferable, Specifically, an acetyloxy group, a propanoyloxy group, butanoyloxy group, a pentanoyloxy group, a trifluoromethylcarbonyloxy group, benzoyloxy group, 1- Naphthylcarbonyloxy group, and 2-naphthylcarbonyloxy group can be illustrated.

The alkylsulfanyl group is preferably an alkylsulfanyl group having 1 to 20 carbon atoms, specifically, methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, isopropylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, cyclohexylsulfanyl group, octyl Sulfanyl group, 2-ethylhexylsulfanyl group, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, and methoxymethylsulfanyl group can be exemplified.

As the arylsulfanyl group, an arylsulfanyl group having 6 to 30 carbon atoms is preferable, and specifically, a phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, 2-chlorophenylsulfanyl group, 2-methylphenylsulfanyl group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group, 4-fluoro A rophenylsulfanyl group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfanyl group, and 4-dimethylaminophenylsulfanyl group are illustrated. Can be.

The carbamoyl group is preferably a carbamoyl group having 1 to 30 carbon atoms in total, and specifically N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-butylcarbamoyl group, and N- Hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group , N-2-chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N- 3-nitrophenylcarbamoyl group, N-3-cyanophenylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarba Barmoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-di Phenylcarbamoyl group It can be poetry.

The sulfamoyl group is preferably a sulfamoyl group having 0 to 30 carbon atoms, and specifically, a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, a N, N-dialkylsulfamoyl group, N, N-diarylsulfamoyl groups, and N-alkyl-N-arylsulfamoyl groups can be exemplified. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butyl sulfamoyl group, N-hexyl sulfamoyl group, N-cyclohexyl sulfamoyl group, N-jade Tilsulfamoyl, N-2-ethylhexylsulfamoyl, N-decylsulfamoyl, N-octadecylsulfamoyl, N-phenylsulfamoyl, N-2-methylphenylsulfamoyl, N-2-chloro Phenyl sulfamoyl group, N-2-methoxyphenyl sulfamoyl group, N-2-isopropoxyphenyl sulfamoyl group, N-3-chlorophenyl sulfamoyl group, N-3-nitrophenyl sulfamoyl group, N- 3-cyanophenylsulfamoyl group, N-4-methoxyphenylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenyl Sulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, and N, N -Diphenylsulfamoyl group can be preferably exemplified.

Preferably an amino group of a total carbon number of 0-50 and, specifically, as the amino group is an amino group (-NH _2), N- alkylamino, N- arylamino group, N- acylamino group, N- sulfonyl amino group, N, N- dialkyl Amino groups, N, N-diarylamino groups, N-alkyl-N-arylamino groups, and N, N-disulfonylamino groups can be exemplified. 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-sia Nophenylamino group, N-3-trifluoromethylphenylamino group, N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenyl Amino group, N-4-phenylsulfanylphenylamino group, N-4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-di Tylamino group, N, N-dibutylamino group, N, N-diphenylamino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N -(Dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) amino group, N, N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group, morpholino group, and 3 , 5-dimethylmorpholino group and carbazole group may be preferably exemplified.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

Among these, as X, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkylsulfanyl group, an arylsulfanyl group, and an amino group are preferable from a viewpoint of solvent solubility and the absorption efficiency improvement of a long wavelength region.

In addition, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

As a bivalent organic group represented by said Y, the structure shown below is mentioned. In addition, in the group shown below, "*" shows the bonding position of the carbon atom adjacent to Y in the said Formula (2).

Especially, the structure shown below is preferable from a viewpoint of high sensitivity.

It is preferable that the specific oxime compound in this invention is a compound represented by following formula (3).

[In Formula (3), R and X respectively independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, n is an integer of 0-5.]

R, X, A, Ar, and n in Formula (3) are synonymous with R, X, A, Ar, and n in said Formula (2), respectively, and a preferable example is also the same.

Hereinafter, although the specific example (K-1)-(K-88) of the specific oxime compound in this invention is shown below, this invention is not limited to these.

It is preferable that the specific oxime compound in this invention has maximum absorption wavelength in the wavelength range of 350 nm-500 nm, It is more preferable to have an absorption wavelength in the wavelength range of 360 nm-480 nm, It is especially preferable that the absorbance of 365 nm and 455 nm is high desirable. In particular, since the specific oxime compound is absorbed in a longer wavelength region than the conventional oxime compound, it exhibits excellent sensitivity when exposed to a light source of 365 nm or 405 nm.

It is preferable that the molar extinction coefficient in 365 nm or 405 nm of the specific oxime compound in this invention is 10,000-300,000, It is more preferable that it is 15,000-300,000, It is especially preferable that it is 20,000-200,000.

In addition, in the present invention, the molar extinction coefficient of the compound may be a known method. Specifically, for example, 0.01 g / L using an ethyl acetate solvent using an ultraviolet visible spectrophotometer (Carry-5 spectrophotometer manufactured by Varian). It is preferable to measure at the concentration of.

Although the specific oxime compound in this invention can be synthesize | combined by the method shown below, for example, it is not limited to this method.

Moreover, the photosensitive resin composition of this invention can use together a sensitizer and a light stabilizer.

Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone , 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-diethyl thioxanthone, acridon, 10-butyl-2-chloro Acridon, benzyl, dibenzylacetone, p- (dimethylamino) phenylstyrylketone, p- (dimethylamino) phenyl-p-methylstyrylketone, benzophenone, p- (dimethylamino) benzophenone (or US Heiler ketone), p- (diethylamino) benzophenone, benzanthrone, the benzothiazole type compound of Unexamined-Japanese-Patent No. 51-48516, etc., Tinuvin 1130, Tinuvin 400, etc. are mentioned.

In addition to the photoinitiator mentioned above, another well-known initiator can be used for the photosensitive resin composition of this invention.

Specifically, bisinal polyketoaldonyl compounds disclosed in US Pat. No. 2,367,660, α-carbonyl compounds disclosed in US Pat. Nos. 2,367,661 and 2,367,670, US Pat. No. 2,448,828 are disclosed. Acyloinethers, aromatic acyloin compounds substituted with α-hydrocarbons disclosed in US Pat. No. 2,722,512, multinuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, US Pat. Combination of triallylimidazole dimer / p-aminophenyl ketone disclosed in the specification of 3,549,367, benzothiazole compound / trihalomethyl-s-triazine system disclosed in Japanese Patent Publication No. 51-48516 Compounds and the like.

The photosensitive resin composition of this invention may contain only 1 type, or may contain 2 or more types of photoinitiators.

As for content (in the case of 2 or more types, total content) of the photoinitiator in the total solid of the photosensitive resin composition of this invention, 1-30 weight% is preferable from a viewpoint of obtaining the effect by this invention more effectively, 2-25 weight % Is more preferable, and 3-20 weight% is especially preferable.

(E) organic solvent

The photosensitive resin composition of this invention contains the organic solvent. An organic solvent can be used individually by 1 type, and may be used in combination of 2 or more type.

Although the organic solvent used for this invention is not specifically limited as long as it satisfies the solubility of each component of (A)-(D) and the application | coating characteristic of the photosensitive resin composition, (A) Dispersibility of titanium black especially, (C) It is preferable to select in consideration of solubility, applicability, and safety of the resin.

Examples of the solvent that can be used 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, and alkyl esters. Methyl lactate, ethyl lactate, methyl oxyacetic acid, ethyl oxyacetic acid, oxyacetic acid butyl, methoxyacetic acid methyl, methoxyacetic acid, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid and the like;

3-oxypropionic acid alkyl esters, such as methyl 3-oxypropionate and ethyl 3-oxypropionate, for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and 3-ethoxypropionic acid Ethyl and the like; 2-oxypropionic acid alkyl esters, such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionic acid, for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, and 2-methoxypropionic acid propyl , Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy Ethyl-2-methylpropionate and the like; Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

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 and the like;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons such as toluene, xylene and the like are preferable.

The photosensitive resin composition of this invention can contain the other organic solvent further.

(F) other ingredients

The photosensitive resin composition of this invention may contain (F) other components in addition to said (A)-(E). (F) As other components, a sensitizer, a sensitizer, a thermal polymerization inhibitor, an adhesion promoter, or other additives can be illustrated.

<Sensitizer>

The photosensitive resin composition of this invention may contain a sensitizer.

As said sensitizer, it is preferable to sensitize the above-mentioned photoinitiator with an electron transfer mechanism or an energy transfer mechanism.

As said sensitizer, what belongs to the compounds listed below, and what has an absorption wavelength in the wavelength range of 300 nm-450 nm are mentioned.

That is, for example, polynuclear aromatics (e.g., phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (e.g., fluorescein, eosin, erythro Shin, rhodamine B, rose bengal), thioxanthones (isopropyl thioxanthone, diethyl thioxanthone, chloro thioxanthone), cyanines (e.g., thiacarbocyanine, oxacarbocyanine) Merocyanines (e.g. merocyanine, carbomerocyanine), phthalocyanines, thiazines (e.g. thionine, methylene blue, toluidine blue), acridines (e.g. Credin orange, chloroflavin, acriflavin), anthraquinones (e.g., anthraquinones), squaraines (e.g., squaria), coumarins (e.g., 7-diethylamino- 4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, tripe Methane, distyrylbenzenes, carbazoles, porphyrins, spiro compounds, quinacridones, indigo, styryls, pyryllium compounds, pyrromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thio Aromatic ketone compounds such as barbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, and heterocyclic compounds such as N-aryloxazolidinone.

When the photosensitive resin composition of this invention contains a sensitizer, content of the sensitizer in the photosensitive resin composition is 0.1-20 weight% with respect to the weight of all solid content from a viewpoint of the light absorption efficiency and starting decomposition efficiency to a core part. It is preferable that it is and 0.5-15 weight% is more preferable.

Notary sensitizer

The photosensitive resin composition of this invention may contain a co-sensitizer.

The sensitizer has an action of further improving the sensitivity of the photopolymerization initiator and the sensitizer to actinic radiation, or inhibiting the inhibition of polymerization of the polymerizable compound by oxygen.

Examples of such a sensitizer include amines such as MR Sander et al., Journal of Polymer Society, Vol. 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japan Japanese Patent Laid-Open No. 52-134692, Japanese Patent Laid-Open No. 59-138205, Japanese Patent Laid-Open No. 60-84305, Japanese Patent Laid-Open No. 62-18537, Japanese Patent Laid-Open No. 64-33104, Research The compound of Disclosure 33825, etc. are mentioned, Specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthio dimethylaniline, etc. are mentioned.

As another example of a sensitizer, thiols and sulfides such as thiol compounds described in Japanese Patent Application Laid-Open No. 53-702, Japanese Patent Application Laid-Open No. 55-500806, Japanese Patent Application Laid-Open No. 5-142772, and Japanese Patent The disulfide compound of Unexamined-Japanese-Patent No. 56-75643, etc. are mentioned, Specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 (3H) -quinazoline, (beta) -mercaptonaphthalene, etc. are mentioned.

Other examples of the co-sensitizer include amino acid compounds (e.g., N-phenylglycine), organometallic compounds (e.g., tributyltin acetate, etc.) described in Japanese Patent Publication No. 48-42965, Japanese Patent Publication No. 55-34414 The hydrogen donor of Unexamined-Japanese-Patent No., the sulfur compound (for example, tritian etc.) of Unexamined-Japanese-Patent No. 6-308727, etc. are mentioned.

When the photosensitive resin composition of this invention contains a sensitizer, content of the said sensitizer is 0.1-with respect to the weight of the total solid of the photosensitive resin composition from a viewpoint of the improvement of the hardening rate by the balance of a polymerization growth rate and a chain transfer. The range of 30 weight% is preferable, The range of 1-25 weight% is more preferable, The range of 0.5-20 weight% is further more preferable.

<Heat polymerization inhibitor>

In the photosensitive resin composition of this invention, a small amount of thermal polymerization inhibitor can be added in order to prevent unnecessary thermal polymerization of a polymeric compound during manufacture or storage of a 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-butyl phenol), N-nitrosophenylhydroxyamine 1st cerium salt, etc. are mentioned.

When the photosensitive resin composition of this invention contains a thermal polymerization inhibitor, the addition amount of a thermal polymerization inhibitor is preferable about 0.01 to about 5 weight% with respect to the total solid of the photosensitive resin composition.

In addition, in order to prevent the inhibition of polymerization by oxygen, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added and localized on the surface of the coating film in 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.

<Adhesion enhancer>

In the photosensitive resin composition of this invention, an adhesion promoter can be added in order to improve adhesiveness with hard surfaces, such as a board | substrate. As an adhesion promoter, a silane coupling agent, a titanium coupling agent, etc. are mentioned.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyl. Trimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxy sisilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyl Trimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyl Trimethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxy Silane, Methyltrimethoxysilane, Methyltriethoxysil , Vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-meth Methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane , Trimethylchlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N -(3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (meth Krilloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane, etc. Can.

Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane and γ-mercaptopropyltri Methoxysilane, (gamma) -aminopropyl triethoxysilane, and phenyl trimethoxysilane are preferable, and (gamma) -methacryloxypropyl trimethoxysilane is the most preferable.

When the photosensitive resin composition of this invention contains an adhesion improving agent, 0.5-30 weight% is preferable and, as for the addition amount of an adhesion improving agent, in the total solid of the photosensitive resin composition, 0.7-20 weight% is more preferable.

<Other additives>

Moreover, about the photosensitive resin composition of this invention, in order to improve the physical property of a cured film, you may add well-known additives, such as an inorganic filler, a plasticizer, and a sensing agent.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetylglycerine, and the like. 10 weight% or less with respect to a non volatile component) can be added.

(Method for Producing Photosensitive Resin Composition)

The photosensitive resin composition of this invention can be prepared by mixing said (A)-(E) and other components (F) as needed, and disperse | distributing titanium black uniformly.

In addition, it is preferable to disperse | distribute titanium black in resin solution previously in presence of a dispersion adjuvant. The step of dispersing the titanium black is preferably carried out in two steps: a step of kneading in a highly viscous resin solution and a step of dispersing a medium using a medium.

In the kneading process of titanium black in the manufacture of the photosensitive resin composition of this invention, titanium black and another combined black color material, a dispersing agent, and / or a surface treatment agent, alkali-soluble resin, and a solvent are kneaded first. The machine used for kneading is not particularly limited, but two rolls, three rolls, ball mills, tron mills, dispersers, kneaders, kneaders, homogenizers, blenders and single or twin screw extruders can be exemplified, and strong shear forces It is preferable to disperse while giving.

Next, an organic solvent and resin (residue used in the kneading process) are added. As a machine used in a dispersion process, a sand grinder, a pin mill, a slit mill, an ultrasonic disperser of a vertical or horizontal type is mainly illustrated, and it disperse | distributes using media (beads), such as glass and zirconia, which have a particle diameter of 0.1-1 mm. It is preferable.

Moreover, it is also possible to omit the said kneading process, and in that case, it is preferable to disperse | distribute a pigment, a dispersing agent, and / or a surface treating agent, resin, and a solvent. In this case, it is preferable to add the remaining resin in the kneading step during the dispersion.

Details of the kneading process and the dispersion process are described in T. C. Patton, "Paint Flow and Pigment Dispersion" (1964, John Wiley and Sons).

(2) light blocking color filter

The photosensitive resin composition of this invention can be used suitably for manufacture of a light-shielding color filter.

In this invention, a "light-shielding color filter" means the light-shielding pattern obtained by apply | coating, exposing, and developing the photosensitive resin composition containing at least a black material, a photopolymerizable compound, resin, a photoinitiator, and 2 or more types of organic solvents. . The color of the "light-shielding color filter" in the present invention may be achromatic, such as black or gray, or may be black, gray, or the like in which the chromatic color is mixed.

In addition, since "the light-shielding color filter" was obtained by apply | coating, exposing, and developing the photosensitive resin composition containing at least a black color material, a photopolymerizable compound, resin, a photoinitiator, and an organic solvent, it replaced with a light-shielding film or a light-shielding filter. You can say it.

Here, it is preferable that the average light transmittance of a light-shielding color filter is 10% or less in visible region and infrared region (400-1,600 nm), and it is more preferable that average transmittance is 1% or less.

It is preferable to provide a light-shielding color filter in the light shielding part of the back surface which opposes the light shielding part periphery of the imaging part of a solid-state image sensor, and / or the surface with an imaging part.

By increasing the light shielding property of the said imaging part peripheral edge light shielding part and / or the imaging surface back surface, the dark current which generate | occur | produces other than an imaging part can be reduced, and the photoelectric conversion function which passed the color filter arrange | positioned at the imaging element can be improved.

Moreover, in this invention, it is preferable that the optical density of the light-shielding color filter formed using the photosensitive resin composition is 2 or more and 10 or less, It is more preferable that it is 3 or more and 10 or less, It is especially preferable that it is 4 or more and 9 or less.

Although there is no limitation in particular as a film thickness of a light-shielding color filter, From a viewpoint of obtaining the effect by this invention more effectively, 0.1 micrometer-10 micrometers are preferable, 0.3 micrometer-5.0 micrometers are more preferable, 0.5 micrometer-3.0 micrometers are especially desirable.

Although there is no limitation in particular as a size (length of one side) of a light-shielding color filter, From a viewpoint of obtaining the effect by this invention more effectively, 200 micrometers or more are preferable, 500 micrometers or more are more preferable, 1,000 micrometers or more are especially preferable. . Although there is no limitation in particular also about an upper limit, 10,000 micrometers is preferable.

The area of the light-shielding color filter is not particularly limited, but from the viewpoint of obtaining the effect of the present invention more effectively, 0.05 mm 2 or more is more preferable, 0.2 mm 2 or more is more preferable, and 1 mm 2 or more is particularly preferable. Although there is no limitation in particular about an upper limit, It is preferable that it is 9 mm <2> or less.

The light-shielding color filter of this invention can be used suitably for solid-state image sensors, such as CCD and CMOS, for example, and is especially preferable for solid-state image sensors, such as CCD and CMOS, which exceed 1 million pixels.

(3) Manufacturing method of light-shielding color filter

Moreover, although the manufacturing method of the light-shielding color filter of this invention is not specifically limited, (a) The process of apply | coating the photosensitive resin composition of this invention to a board | substrate (photosensitive layer formation process), (b) The process of image exposure (exposure process) ) And (c) development and patterning step (development step).

Hereinafter, each process in the manufacturing method of the light-shielding color filter of this invention is demonstrated.

(a) photosensitive layer forming process

In the photosensitive layer formation process, the photosensitive resin composition of this invention is apply | coated on a board | substrate, and a photosensitive layer is formed.

As a board | substrate which can be used for this process, the photoelectric conversion element board used for a solid-state image sensor etc., for example, a silicon board | substrate, a complementary metal oxide film semiconductor (CMOS), etc. are mentioned, for example.

Furthermore, on these board | substrates, you may form an undercoat layer as needed in order to improve adhesiveness with an upper layer, to prevent the spread of a substance, or to planarize a substrate surface.

As a coating method of the photosensitive resin composition of this invention on a board | substrate, various coating methods, such as a slit application | coating, an inkjet method, a rotary application | coating, cast | coating application | coating, roll coating, and screen printing, can be applied.

As a coating film thickness of the photosensitive resin composition, 0.35 micrometers-3.0 micrometers are preferable from a viewpoint of resolution and developability, and 0.50 micrometers-2.5 micrometers are more preferable.

The photosensitive resin composition apply | coated on the board | substrate is dried under the conditions of about 2 minutes-about 4 minutes at 70 degreeC-110 degreeC normally, and a photosensitive layer is formed.

(b) exposure process

In an exposure process, the photosensitive layer formed in the said photosensitive layer formation process is exposed and hardened | cured. In this invention, it is preferable that it is a process of exposing through a mask, and it is more preferable that it is a process 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.

It is preferable to perform exposure by irradiation of radiation, and as radiation which can be used at the time of exposure, especially ultraviolet rays, such as g line (436 nm) and i line (365 nm), are used preferably, and i line | wire is used more preferably. As the light source, a high pressure mercury lamp is more preferable. The irradiation intensity is preferably 5 mJ to 1500 mJ, more preferably 10 mJ to 1,000 mJ, and most preferably 10 mJ to 800 mJ.

(c) developing process

You may perform an alkali image development process (development process) following an exposure process.

In the image development process, the non-irradiated part in an exposure process is eluted to an alkali aqueous solution. This leaves only the photocured portion.

As a developing solution, the organic alkali developing solution which does not cause damage to a circuit of an underlayer etc. is preferable. As image development temperature, it is 20 degreeC-30 degreeC normally, and developing time is 20 to 90 second.

As an alkali used for a developing solution, for example, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-dia An alkaline aqueous solution obtained by diluting an organic alkaline compound such as xabicyclo- [5,4,0] -7-undecene to a concentration of 0.001 to 10% by weight, preferably 0.01 to 1% by weight is used. In addition, when the developing solution which consists of such alkaline aqueous solution is used, generally it wash | cleans (rinses) with pure water after image development.

Moreover, in the manufacturing method of the light-shielding filter for solid-state image sensors of this invention, after performing the photosensitive layer formation process, exposure process, and image development process mentioned above, the hardening process of hardening the pattern formed as needed by heating and / or exposure is carried out. You may include it.

The heating process (post-baking process) after a image development process is heating after image development to complete hardening, and it is preferable to perform the heating (hard bake) at 180 degreeC-250 degreeC. This post-baking process can be performed continuously or batchwise using heating means, such as a hotplate, a convection oven (hot air circulation type dryer), and a high frequency heater, so that the coating liquid after image development may become said temperature condition.

Moreover, you may harden a coloring pattern by irradiating an ultraviolet-ray with a high pressure mercury lamp etc. independently of the said post-baking process (postcure process).

(4) solid-state imaging device

The photosensitive resin composition of this invention can be used suitably for solid-state image sensors. Specifically, after apply | coating the photosensitive resin composition of this invention as a thin film on a board | substrate, the light-shielding color filter which has a desired shape can be manufactured by image-exposure by i line | wire etc., and developing and patterning.

In addition, as already demonstrated, a light-shielding color filter means the light-shielding pattern obtained by exposing and developing the photosensitive resin composition containing at least a black color material, a photopolymerizable compound, resin, a photoinitiator, and a solvent. The color of the "light-shielding color filter" in the present invention may be achromatic, such as black or gray, or may be black, gray, or the like in which the chromatic color is mixed. Moreover, it is preferable that it is a filter whose average transmittance is 10% or less in visible region and an infrared region (400-1,600 nm), and it is more preferable that average transmittance is 1% or less.

The solid-state image sensor of this invention is equipped with the said light-shielding color filter. It is characterized by the above-mentioned.

Hereinafter, the solid-state imaging device will be described with reference to the drawings.

BRIEF DESCRIPTION OF THE DRAWINGS 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 circumferential edge. An example of the solid-state image sensor which has the light-shielding color filter which photocured the solid content of the photosensitive resin composition of this invention in the periphery of the color filter which comprises a three primary color pixel is shown in FIG.

In FIG. 1, the solid-state imaging device 1 has a photoelectric conversion element (light receiving sensor portion) 12 on the silicon substrate 10. In addition, transfer electrodes 14a and 14b are provided adjacent to the photoelectric conversion element 12 to transfer generated charges. The transfer electrodes 14a and 14b are covered with the insulating film 16.

On the photoelectric conversion element 12, color filters 4R, 4G, and 4B which regularly arrange three primary color pixels consisting of three primary colors of R (red), G (green), and B (blue) are disposed and photographed. The part 2 is formed. At the peripheral edge of this imaging part 2, the light shielding part 3 provided with the light-shielding color filter 5 formed by photocuring the photosensitive resin composition of this invention is formed.

In FIG. 1, the photoelectric conversion element 12, such as CCD or CMOS, the transfer electrodes 14a and 14b, the planarization layer 18a, etc. which are needed as the solid-state image sensor 1 can be formed in accordance with a well-known IC manufacturing method. have. In addition, the color filters 4R, 4G, 4B and the light blocking color filter 5 can be formed by photoresist technology. The planarization layer 18b may also be formed on the color filters 4R, 4G, and 4B. In addition, it is preferable to provide a microlens 17 on the color filters 4R, 4G, and 4B for condensing.

The photosensitive resin composition containing titanium black as a light-shielding agent of visible light and infrared light is uniformly applied on the silicon substrate 10 having the color filters 4R, 4G, and 4B, and heated to form a dry coating film. Subsequently, exposure is carried out using a commercially available i-ray stepper or the like through a mask in which a mask pattern is formed to open the image capturing unit 2 in the dry coating film and cover the photoelectric conversion element or the like used for dark current measurement. The pattern of the light-shielding color filter 5 can be obtained by washing with water and drying.

Furthermore, after forming the planarization layer 18b and the microlens 17 on the obtained board | substrate as needed, the solid-state imaging element 1 is obtained by dicing and packaging.

At this time, 5 micrometers or less are preferable, as for the film thickness of the optical function layer from the silicon substrate surface to a microlens lower surface, 4.5 micrometers or less are more preferable, 4 micrometers or less are especially preferable.

In the solid-state imaging device of the present invention, as described above, in addition to disposing the light-shielding color filter on the peripheral edge of the imaging unit, it is preferable to further arrange the light-shielding color filter on the rear surface facing the surface with the imaging unit.

Specifically, in the solid-state imaging device having a plurality of projection electrodes for connecting to the wiring board 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 projection electrodes on the back surface.

Background Art Conventionally, in a solid-state imaging device having projection electrodes on the back surface, stray light enters into the solid-state imaging device from between the solid-state imaging device and the solid-state imaging device wiring board, and a dark current is generated, which tends to deteriorate the captured image. The solid-state image sensor of this invention can also prevent intrusion of this stray light by providing a light shielding color filter on the back surface. Therefore, generation of dark current by stray light from the back surface side can be suppressed and color reproducibility can be improved, even if omission of the light-shielding underfill resin etc. which are conventionally performed for the intrusion of stray light is omitted.

EMBODIMENT OF THE INVENTION Preferred embodiment of the solid-state image sensor of this invention is described, referring FIG. 2 and FIG. 2 is a configuration diagram showing an example of the solid-state imaging device of the present invention. 3 is a cross-sectional view of AA ′ in FIG. 2.

As shown in FIG. 2, the solid-state imaging device 20 includes a solid-state imaging device 24 having an imaging section 2, a light shielding section 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. 2. The solid-state imaging device 24 includes an imaging section 2 and a light shielding section 3 on its surface, and further includes a light shielding color filter 23 and a projection electrode 26 on its rear surface. In addition, the underfill resin 25 may be provided between the solid-state imaging element 24 and the wiring board 21 for the purpose of improving durability and preventing stray light.

The through electrode 27 is formed under the bonding pad 30 formed in the solid-state imaging element 24, and is connected to the projection electrode 26 provided in the back surface of the solid-state imaging element 24.

The solid-state imaging element 24 can be connected to the wiring board 21 via the plurality of protruding electrodes 26. Although the well-known thing can be used as the projection electrode 26, It is not limited, For example, a solder ball, a gold stud bump, a gold plating bump, etc. are mentioned.

When the light-shielding color filter 23 is arrange | positioned on the back surface of the solid-state image sensor 24 of this invention, the dark current which a imaging light enters a solid-state image sensor as stray light can be reduced.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example. In addition, "part" "percentage (%)" is a basis of weight unless there is particular notice.

(1) Preparation of Titanium Black Dispersion

<Production of Titanium Black Crude Dispersion>

The crude dispersion of titanium black was produced by performing a high viscosity dispersion process using two rolls to the following composition. The viscosity of the obtained crude dispersion was 40,000 mPa · s.

Moreover, you may knead | mix for 30 minutes with a kneader before a high viscosity dispersion process.

Titanium Black Coarse Dispersion Composition

Jemco Inc. Product Titanium Black 13M-T: 40 parts

Propylene glycol monomethyl ether acetate solution of benzyl methacrylate / methacrylic acid copolymer {BzMA / MAA = 70/30 (molar ratio), Mw: 30,000, solid content 40 wt%}: 6 parts

Solsperth 5000 (from Zenca): Part 1

The following component (A) was added to the obtained titanium black coarse dispersion, and it stirred for 3 hours using the homogenizer on the conditions of 3,000 rpm. The obtained mixed solution was dispersed for 4 hours using a disperser (Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads to obtain a titanium black dispersion. The viscosity of this dispersion liquid was 8.0 mPa * s.

[Component (A)]

Propylene glycol monomethyl ether acetate solution of benzyl methacrylate / methacrylic acid copolymer {BzMA / MAA = 70/30 (molar ratio), Mw: 30,000, solid content 40 wt%}: 10 parts

Organic solvent (propylene glycol monomethyl ether acetate): 140 parts

Example 1

(2) Preparation of Photosensitive Resin Composition

Each component shown below was mixed and the photosensitive resin composition was prepared.

Methyl methacrylate / methacrylic acid terpolymer ({following (J-1)}): 6.1 parts

Dipentaerythritol hexaacrylate (T-1): 4.8 parts

Ethoxylated pentaerythritol tetraacrylate (T-2): 1.7 parts

The titanium black dispersion: 67 parts

Propylene Glycol Monomethyl Ether Acetate (PGMEA): 15.7 parts

Oxime photoinitiator (K-1): 1.7 parts

(Example 2)

The photosensitive resin composition for light shielding film formation was produced like Example 1 except having used the photoinitiator (K-2) instead of the oxime system photoinitiator (K-1).

(Example 3)

The photosensitive resin composition for light shielding film formation was produced like Example 1 except having used the photoinitiator (K-3) instead of the oxime system photoinitiator (K-1).

(Example 4)

A resin composition for forming a light shielding film was produced in the same manner as in Example 1 except that (T-3) was used instead of (T-2).

(Example 5)

Except having used (T-4) instead of (T-2), it carried out similarly to Example 1, and produced the resin composition for light shielding film formation.

(Example 6)

A resin composition for forming a light shielding film was produced in the same manner as in Example 1 except that (T-1) 4.0 parts and (T-2) 2.5 parts were used instead of 4.8 parts of (T-1) and 1.7 parts of (T-2). .

(Comparative Example 1)

A photosensitive resin composition for light-shielding films was prepared in the same manner as in Example 1 except that 4.8 parts of the photopolymerizable compound (T-1) and 1.7 parts of the photopolymerizable compound (T-2) were used. did.

(Comparative Example 2)

A photosensitive resin composition for light-shielding films was prepared in the same manner as in Example 1 except that 4.8 parts of the photopolymerizable compound (T-1) and 6.5 parts of the photopolymerizable compound (T-2) were used instead of 4.8 parts of the photopolymerizable compound (T-1). did.

(3) Fabrication of light shielding film and evaluation thereof

The obtained photosensitive resin composition was apply | coated to the 8-inch silicon wafer by the spin coat method, and it heated at 120 degreeC on the hotplate for 2 minutes after that.

Subsequently, an i-line stepper was used to expose the pattern of 3 mm in all directions from 100 mJ / cm 2 to 1,000 mJ / cm 2 in steps of 100 mJ / cm 2.

After irradiation, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide (CD-2060 manufactured by FFEM). Thereafter, the water was rinsed with a spin shower.

The obtained pattern was observed with the optical microscope and the length measurement SEM, and adhesive evaluation was performed.

In addition, each photosensitive resin composition was applied to a separate 8-inch silicon wafer at 1,500 rpm (dry film thickness of 2.0 µm), the film thicknesses of the center portion and the edge vicinity were measured, and the difference thereof was calculated as an index of coating film thickness uniformity. did. The smaller the numerical value, the better the coating film uniformity.

As shown in Table 1, when two or more types of polymerizable compounds were used together as the polymerizable compound, the amount of irradiation yielded better adhesion than the data using the polymerizable compound alone was small, and the uniformity of the coating film thickness was also good.

Claims (12)

(A) titanium black, (B) two or more polymerizable compounds, (C) resin, (D) a photopolymerization initiator, and (E) At least the organic solvent is contained, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1, (B) 2 or more types of polymeric compounds containing 2 or more types of polymeric compounds which have a different number of ethylenically unsaturated groups in 1 molecule, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1, (B) 2 or more types of polymeric compounds containing the complete (meth) acrylic acid ester of 2 or more types of aliphatic polyol which has a different number of hydroxyl groups, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1, (B) Photosensitive resin composition containing (meth) acrylic acid ester of pentaerythritol and / or dipentaerythritol as 2 or more types of polymeric compounds. The method of claim 1, (D) Photosensitive resin composition containing an oxime initiator as a photoinitiator. The method of claim 5, wherein The said oxime system initiator is represented by following formula (1), The photosensitive resin composition characterized by the above-mentioned. [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 method of claim 5, wherein The said oxime system initiator is represented by following formula (2), The photosensitive resin composition characterized by the above-mentioned. [In Formula (2), R and X respectively independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, n is an integer of 0-5.] The method of claim 5, wherein The said oxime system initiator is represented by following formula (3), The photosensitive resin composition characterized by the above-mentioned. [In Formula (3), R and X respectively independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, n is an integer of 0-5.] The method of claim 1, It is for a solid-state image sensor, The photosensitive resin composition characterized by the above-mentioned. It has a pattern formed using the photosensitive resin composition in any one of Claims 1-9, The light-shielding color filter characterized by the above-mentioned. The process of apply | coating the photosensitive resin composition of any one of Claims 1-9 to a board | substrate, An image exposure step, and The manufacturing method of the light-shielding color filter characterized by including the process of developing and patterning. It has the light-shielding color filter of Claim 10, The solid-state image sensor characterized by the above-mentioned.