JP5326419B2 - Radiation-sensitive composition for forming light-shielding film, light-shielding film for solid-state image sensor, and solid-state image sensor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive composition for forming a light-shielding film capable of forming a light-shielding film excellent in light-shielding performance and bondability on the circumferential edge of an effective pixel region (image capturing part) of a solid-state image sensor such as a CCD or a CMOS, and enabling the obtained light-shielding film to maintain the above performance even in a condition of a high humidity and a high temperature, to provide a light-shielding film for a solid-state image sensor, and to provide a solid-state image sensor. <P>SOLUTION: The radiation-sensitive composition for forming a light-shielding film is used to form a light-shielding film on the circumferential edge of an effective pixel region of the solid-state image sensor. The composition contains: a black pigment, a modified acrylic block polymer having acid number of 15-40 mgKOH/g and amine number of 25-40 mgKOH/g, an alkali-soluble resin having a repetitive structure unit derived from acenaphtylene or N-phenylmaleimide, a polyfunctional monomer, and a photopolymerization initiator. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a radiation-sensitive composition for forming a light-shielding film used for forming a light-shielding film on the periphery of an effective pixel region (imaging unit) of a solid-state image sensor such as a CCD or CMOS, a light-shielding film for a solid-state image sensor, and The present invention relates to a solid-state imaging device.

  In recent years, the performance of electronic devices such as digital cameras, video cameras, in-vehicle cameras, personal computers having photographing functions, mobile phones, electronic notebooks, etc., equipped with solid-state imaging devices including solid-state imaging devices such as CCDs and CMOSs has been rapidly improved. . In this solid-state imaging device, it is unnecessary for the photoelectric conversion unit included in the solid-state imaging device in order to reduce the dark current, prevent the dynamic range from being lowered, stabilize the operation of the peripheral circuit, and suppress the degradation of the image quality. It is common to block light and is known, for example, in US Pat. In these documents, a light-shielding film that includes a black colorant and a resin and is disposed at the periphery of an effective pixel region (imaging unit) of a photoelectric conversion unit in a solid-state imaging device is disclosed. Patent Document 3 discloses a binder resin, a photoacid generator that absorbs light to generate an acid, a crosslinking agent that crosslinks by the action of the photoacid generator, and metal particles and / or metal compound particles. The photosensitive resin composition for light shielding films to contain is disclosed.

JP 2006-156801 A JP 2007-115921 A JP 2006-284947 A

The above electronic devices have come to be used in various environments as the performance improves, and in particular, under conditions of low temperature to high temperature and high humidity, the light shielding property and the adhesiveness do not deteriorate. There has been a demand for a light-shielding film that provides a solid-state imaging device having stable performance.
An object of the present invention is to form a light-shielding film excellent in light-shielding property and adhesion on the periphery of an effective pixel region (imaging part) of a solid-state image sensor such as a CCD or CMOS. Another object of the present invention is to provide a radiation-sensitive composition for forming a light-shielding film, a light-shielding film for a solid-state image sensor, and a solid-state image sensor that can maintain the above performance even under conditions of high temperature and high humidity.

The present invention is shown below.
1. A radiation-sensitive composition for forming a light-shielding film used for forming a light-shielding film on the periphery of an effective pixel region in a solid-state imaging device, wherein (A) a black pigment and (B) an acid value of 15 to 40 mgKOH / g And a modified acrylic block copolymer having an amine value of 25 to 40 mg KOH / g, (C) an alkali-soluble resin having a repeating structural unit derived from acenaphthylene or N-phenylmaleimide, (D) a polyfunctional monomer, and , (E) a photopolymerization initiator, and the content of the (A) black pigment is 100 parts by mass in total of the (C) alkali-soluble resin and the (D) polyfunctional monomer. On the other hand, the radiation sensitive composition for light shielding film formation characterized by being 70-300 mass parts .
2. 2. The radiation-sensitive composition for forming a light-shielding film according to 1 above, wherein the black pigment is carbon black and / or titanium black.
3. A light-shielding film for a solid-state imaging device, wherein the light-sensitive composition for forming a light-shielding film according to the above 1 or 2 is used and disposed on the periphery of the effective pixel region.
4). 4. The light shielding film for a solid-state imaging device according to the above 3, wherein the light shielding film has a thickness of 3 μm or less.
5. 5. A solid-state imaging device, wherein the light-shielding film for the solid-state imaging device according to 3 or 4 is disposed on a periphery of the effective pixel region.
6). 6. The solid-state imaging device according to 5 above, wherein the maximum side of the rectangular unit pixel of the color filter corresponding to the photoelectric conversion unit included in the solid-state imaging device is 5 μm or less.

According to the radiation-sensitive composition for forming a light-shielding film of the present invention, a light-shielding film having excellent light-shielding properties and adhesion to light having a wavelength of 400 to 1,600 nm is formed around the effective pixel region in the solid-state imaging device. Even if the obtained light-shielding film is under conditions of low temperature to high temperature and high humidity, for example, at a temperature of −50 ° C. to 230 ° C. and a humidity of 10 to 130%, the above performance (light shielding properties and adhesion) ) Can be maintained. Therefore, by suppressing the transmission (intrusion) of light, it is possible to obtain a solid-state imaging device in which dark current generated in an internal electric circuit or the like is reduced. Further, when the black pigment is carbon black and / or titanium black, the light shielding property is particularly excellent.
According to the light-shielding film for a solid-state image pickup device of the present invention, the solid-state image pickup device and the solid-state image pickup excellent in sustainability of the expected performance are excellent in light-shielding property and adhesion even under conditions of low temperature to high temperature and high humidity. Give device.
Moreover, according to the solid-state imaging device of the present invention, the light-shielding film included therein is excellent in sustainability of desired performance because peeling is suppressed even under conditions of low temperature to high temperature and high humidity.

  The present invention will be described in detail below. In this specification, “(meth) acryl” means acryl and methacryl, and “(meth) acrylate” means acrylate and methacrylate.

  The radiation-sensitive composition for forming a light-shielding film of the present invention is a composition used for forming a light-shielding film on the periphery of an effective pixel region in a solid-state imaging device, and comprises (A) a black pigment (hereinafter, “component” (B) modified acrylic block copolymer having an acid value of 15 to 40 mg KOH / g and an amine value of 25 to 40 mg KOH / g (hereinafter also referred to as “component (B)”). , (C) an alkali-soluble resin having a repeating structural unit derived from acenaphthylene or N-phenylmaleimide (hereinafter also referred to as “component (C)”), (D) a polyfunctional monomer (hereinafter referred to as “component ( D) ”) and (E) a photopolymerization initiator (hereinafter also referred to as“ component (E) ”).

  The component (A) is not particularly limited, and examples thereof include carbon black, titanium black, iron oxide, manganese oxide, and graphite. Of these, carbon black and titanium black are preferable, and carbon black is particularly preferable.

  Examples of the carbon black include furnace black, thermal black, and acetylene black.

Further, as the carbon black, trade names of Mitsubishi Chemical Corporation, # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88 # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Black N339, Da 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; Product name, Thermax N990, N991, N907, N908, N990, N991, N908; product name, Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66 Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal; Degussa Product name, ColorBlack Fw200, ColorBlack Fw2, ColorBla ck Fw2V, ColorBlack Fw1, ColorBlack Fw18, ColorBlack S170, ColorBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, Pr, 140
Furthermore, JP-A-11-60988, JP-A-11-60989, JP-A-10-330643, JP-A-11-80583, JP-A-11-80584, JP-A-9-124969, Resin-coated carbon black disclosed in JP-A-9-95625 and JP-A-9-71733 can also be used.

The carbon black preferably has an insulating property. Insulating carbon black refers to carbon black that exhibits insulating properties when the volume resistance as a powder is measured by the following method, that is, the volume resistance value is 10 ⁶ Ω · cm or more. Yes, for example, it means having an organic compound on the surface of the carbon black particles, for example, an organic substance is adsorbed, coated or chemically bonded (grafted) on the surface of the carbon black particles.
Propylene is used in a mass ratio of 20:80 to a copolymer (weight average molecular weight of 30,000) containing carbon black and a repeating structural unit derived from benzyl methacrylate and methacrylic acid in a molar ratio of 70:30. Disperse in glycol monomethyl ether to obtain a dispersion. Thereafter, this dispersion is applied onto a chromium substrate having a thickness of 1.1 mm and 10 cm × 10 cm to prepare a coating film having a dry film thickness of 3 μm. Subsequently, this coating film is heat-treated in an oven at 200 ° C. for 1 hour. And it applies using the high resistivity meter made from Mitsubishi Chemical Corporation ("High Lester UP (MCP-HT450)") based on JISK6911, volume resistance under the conditions of temperature 23 degreeC and relative humidity 65%. Measure the value.
In the present invention, the preferred volume resistance value of carbon black is preferably 10 ⁸ Ω · cm or more, more preferably 10 ⁹ Ω · cm or more.

Further, as the titanium _{black, TiO, TiO 1.25, Ti 2} O 3, Ti 4 O 7, Ti 3 O 5 , etc. _{(Ti x O y; 1 ≦} x ≦ 4,1 ≦ y ≦ 7, y / x <1.75) low order titanium oxide; titanium nitride; TiO _x N _y (0.2 <x <0.8, 0.6 <y <1.2) titanium oxynitride and the like.
The low-order titanium oxide is obtained by heating titanium dioxide and metallic titanium powder described in Japanese Patent Publication No. 52-12733 in a vacuum or reducing atmosphere at a temperature of 550 ° C. to 1,100 ° C. Compound: Inactive in the presence of a calcination aid consisting of a compound containing silicon, aluminum, niobium, tungsten, etc., as described in JP-A-64-11572. Examples thereof include compounds obtained by heating in an atmosphere.
In addition, as titanium oxynitride, a powder of titanium dioxide or titanium hydroxide described in Japanese Patent Publication No. 3-51645, Japanese Patent Publication No. 2-42773, etc. is about 550 ° C. to 950 ° C. in the presence of ammonia. And compounds obtained by reduction at a temperature of

In addition, as the titanium black, trade names of Mitsubishi Materials Corporation, 10S, 12S, 13M, 13M-C, 13R, 13R-N; trade names of Ako Kasei Co., Ltd., TilacD ultrafine particle type, and the like can be used. .
In addition, the said titanium black can also use the surface-treated thing.

  The number average particle size of the component (A) is preferably 40 nm or less, more preferably 5 to 40 nm, still more preferably 5 to 30 nm, from the viewpoints of dispersion stability and sedimentation prevention. In addition, the said number average particle diameter can be made into the value measured using the electron microscope.

Content of the said black pigment (A) contained in the radiation sensitive composition for light shielding film formation of this invention is 100 mass parts in total of the said alkali-soluble resin (C) and a polyfunctional monomer (D). in contrast, a 70 to 300 parts by weight, more preferably 70 to 250 parts by weight, more preferably from 100 to 200 parts by weight. When content of the said component (A) exists in the said range, it is excellent in the light-shielding property of the light shielding film obtained. That is, the transmittance when a light shielding film having a thickness of 1.4 μm is irradiated with light having a wavelength of 1,200 nm at a temperature of 23 ° C. is preferably 1.5% or less, more preferably 1.3% or less, and further Preferably it can be 1.2% or less. If the content of the component (A) is too small, the thickness of the light shielding film must be increased unnecessarily in order to obtain a high optical density. On the other hand, if the content of the component (A) is too large, curing does not proceed sufficiently, and if the strength as a light shielding film is not sufficient, the development latitude may be narrowed during alkali development.

  The component (B) is a modified acrylic block copolymer having an acid value of 15 to 40 mgKOH / g and an amine value of 25 to 40 mgKOH / g. This component (B) is used as a dispersant for the component (A) to modify the surface of the component (A) to prevent aggregation and sedimentation, and in the radiation sensitive composition for forming a light shielding film of the present invention. The dispersion stability of the components (C) to (E) can be maintained.

  The content of the modified acrylic block copolymer (B) contained in the radiation-sensitive composition for forming a light-shielding film of the present invention is preferably 1 to 40 with respect to 100 parts by mass of the black pigment (A). It is 5 mass parts, More preferably, it is 5-30 mass parts, More preferably, it is 10-25 mass parts. When content of the said component (B) exists in the said range, it is excellent in the light-shielding property of the light shielding film obtained. In addition, when there is too little content of the said component (B), the said component (A) will aggregate and there exists a tendency for a dispersion stability to fall. On the other hand, when there is too much content of the said component (B), component (C)-(E) required for bridge | crosslinking will fall, and there exists a tendency for film | membrane intensity | strength to fall.

  The component (C) is an alkali-soluble resin having a repeating structural unit derived from acenaphthylene or N-phenylmaleimide. That is, the component (C) may be a resin (hereinafter referred to as “resin (C1)”) having a repeating structural unit derived from acenaphthylene (hereinafter referred to as “unit (c1)”), and N. -It may be a resin (hereinafter referred to as "resin (C2)") having a repeating structural unit derived from phenylmaleimide (hereinafter referred to as "unit (c2)"). The component (C) may be a resin containing units (c1) and (c2).

The resin (C1) is a resin containing the unit (c1) with respect to the total amount of the repeating structural units, preferably 5% by mass or more, more preferably 10 to 50% by mass, and still more preferably 15 to 45% by mass. is there. When an alkali-soluble resin having a content of the unit (c1) in the above range is used, a light-shielding film having excellent adhesion can be formed.
The resin (C1) may be a resin composed only of the unit (c1) as described above, or may be a resin composed of the unit (c1) and another unit. Monomers that form other units include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, trivalent or higher unsaturated polycarboxylic acids, and mono (2-acryloyloxyethyl) esters of non-polymerizable dicarboxylic acids. Or a carboxyl group-containing unsaturated compound such as a mono (2-methacryloyloxyethyl) ester, a carboxyl group and a polycaprolactone derivative having a polymerizable unsaturated bond; an unsaturated dicarboxylic acid anhydride, a trivalent or higher unsaturated polyvalent Unsaturated polycarboxylic acid anhydrides such as carboxylic acid anhydrides; aromatic vinyl compounds; unsaturated carboxylic acid esters; unsaturated carboxylic acid aminoalkyl esters; unsaturated carboxylic acid glycidyl esters; carboxylic acid vinyl esters; ; Vinyl cyanide compound; unsaturated amide; aliphatic conjugated diene compound; macromonomer etc. It is below. These may be used alone or in combination of two or more.

Among the carboxyl group-containing unsaturated compounds, examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, α-chloroacrylic acid and the like.
Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid and the like.
As mono (2-acryloyloxyethyl) ester or mono (2-methacryloyloxyethyl) ester of non-polymerizable dicarboxylic acid, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyl) Roxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like.
Examples of the polycaprolactone derivative having a carboxyl group and a polymerizable unsaturated bond include ω-carboxypolycaprolactone mono (meth) acrylate.

Examples of the unsaturated dicarboxylic anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, Indene, p-vinylbenzyl methyl ether, p-vinylbenzyl glycidyl ether and the like can be mentioned.

  Examples of the unsaturated carboxylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec -Butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy dipropylene glycol (meth) acrylate, glycerin mono (meth) acrylate.

Examples of the unsaturated carboxylic acid aminoalkyl ester include 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3 -Aminopropyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, etc. are mentioned.
Examples of the unsaturated carboxylic acid glycidyl ester include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, 3 -Ethyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meth) acrylate, 2,3-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meta ) Acrylate and the like.
Examples of the carboxylic acid vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate.

Examples of the unsaturated ether include vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, and methallyl glycidyl ether.
Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and the like.
Examples of the unsaturated amide include (meth) acrylamide, α-chloroacrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N-methylol (meth) acrylamide and the like.

Examples of the aliphatic conjugated diene compound include 1,3-butadiene, isoprene, chloroprene and the like.
Moreover, as said macromonomer, macromonomers which have a mono (meth) acryloyl group in polymer molecular chain terminal, such as polystyrene, poly (meth) acrylate methyl, poly (meth) acrylate n-butyl, polysiloxane, etc. Etc.

Examples of the resin (C1) include acenaphthylene / methacrylic acid / benzyl methacrylate copolymer, acenaphthylene / methacrylic acid / methyl methacrylate copolymer, acenaphthylene / α-chloroacrylic acid / o-methoxystyrene copolymer, acenaphthylene / acrylic acid.・ Indene copolymer, (meth) acrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate, acenaphthylene, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate copolymer, acenaphthylene, methacrylic acid, N- Examples thereof include a phenylmaleimide copolymer.
The resin (C1) may be used alone or in combination of two or more.

On the other hand, the resin (C2) contains the unit (c2) in an amount of preferably 5% by mass or more, more preferably 10 to 50% by mass, and still more preferably 15 to 45% by mass with respect to the total amount of the repeating structural units. Resin. When an alkali-soluble resin having a content of the unit (c2) in the above range is used, a light-shielding film having excellent adhesion can be formed.
The resin (C2) may be a resin composed only of the unit (c2) as described above, or may be a resin composed of the unit (c2) and another unit. Monomers that form other units include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, trivalent or higher unsaturated polycarboxylic acids, and mono (2-acryloyloxyethyl) esters of non-polymerizable dicarboxylic acids. Or a carboxyl group-containing unsaturated compound such as a mono (2-methacryloyloxyethyl) ester, a carboxyl group and a polycaprolactone derivative having a polymerizable unsaturated bond; an unsaturated dicarboxylic acid anhydride, a trivalent or higher unsaturated polyvalent Unsaturated polycarboxylic acid anhydrides such as carboxylic acid anhydrides; aromatic vinyl compounds; unsaturated carboxylic acid esters; unsaturated carboxylic acid aminoalkyl esters; unsaturated carboxylic acid glycidyl esters; carboxylic acid vinyl esters; ; Vinyl cyanide compound; unsaturated amide; aliphatic conjugated diene compound; macromonomer etc. It is below. These may be used alone or in combination of two or more.

Examples of the resin (C2) include (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / styrene / phenyl (meth) acrylate / N-phenylmaleimide copolymer (Meth) acrylic acid / glycerol mono (meth) acrylate / styrene / N-phenylmaleimide copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer , (Meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / styrene / phenyl (meth) acrylate / N-phenylmaleimide / polystyrene macro Mo Mer copolymer, (meth) acrylic acid / styrene / phenyl (meth) acrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / glycerol mono (meth) acrylate / styrene / methyl ( (Meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / glycerol mono (meth) acrylate / styrene / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / Glycerol mono (meth) acrylate / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / glycerol mono (meth) acrylate / styrene / phenyl (meth) acrylate / N-phenylmaleimi Copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / glycerol mono (meth) acrylate / styrene / N-phenylmaleimide copolymer, (meth) acrylic acid / glycerol mono (Meth) acrylate / styrene / N-phenylmaleimide / polystyrene macromonomer copolymer, (meth) acrylic acid / glycerol mono (meth) acrylate / styrene / N-phenylmaleimide / polymethylmethacrylate macromonomer copolymer, (meta Acrylic acid, styrene, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, N-phenylmaleimide, polystyrene macromonomer copolymer, (meth) acrylic acid, styrene, 2-hydroxyethyl (meth) acrylate, Be Nyl (meth) acrylate / N-phenylmaleimide / polymethylmethacrylate macromonomer copolymer, (meth) acrylic acid / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide / polystyrene macro Monomer copolymers, (meth) acrylic acid, styrene, 2-hydroxyethyl (meth) acrylate, phenyl (meth) acrylate, N-phenylmaleimide, polymethylmethacrylate macromonomer copolymer, and the like.
The resin (C2) may be used alone or in combination of two or more.

  The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC) of the component (C) is preferably 3,000 to 300,000, more preferably 5,000 to 100. 5,000, more preferably 5,000 to 50,000. When Mw of the said component (C) exists in the said range, film strength, such as a patterning characteristic and hardness, heat resistance, water resistance, moisture resistance, can be made compatible.

  The content of the alkali-soluble resin (C) contained in the radiation-sensitive composition for forming a light-shielding film of the present invention is preferably 6 to 160 parts by mass with respect to 100 parts by mass of the black pigment (A). Preferably it is 8-120 mass parts, More preferably, it is 10-80 mass parts. When the content of the component (C) is in the above range, the alkali developability is excellent. In addition, when there is too little content of the said component (C), alkali developability may fall or a ground stain, a film | membrane residue, etc. may generate | occur | produce in an unexposed part. On the other hand, when there is too much content of the said component (C), the target color density may not be obtained.

The component (D) is a monomer having two or more polymerizable unsaturated bonds.
Examples of the component (D) include di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol; di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; glycerin, trimethylolpropane, pentaerythritol, Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as dipentaerythritol and their dicarboxylic acid modified products; oligo (meth) acrylates such as polyesters, epoxy resins, urethane resins, alkyd resins, silicone resins, and spirane resins; Di (meth) acrylates of hydroxylated polymers at both ends, such as terminal hydroxypoly-1,3-butadiene, both ends hydroxypolyisoprene, both ends hydroxypolycaprolactone; 2-acryloyloxyethyl) phosphate, it may be mentioned tris (2-methacryloyloxyethyl) phosphate and the like. These may be used alone or in combination of two or more.

Of the above component (D), poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid modified products are preferred. These compounds include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, In addition to dipentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate, compounds represented by the following formula are preferred.

  The content of the polyfunctional monomer (D) contained in the radiation-sensitive composition for forming a light-shielding film of the present invention is preferably 25 to 400 with respect to 100 parts by mass of the alkali-soluble resin (B). It is a mass part, More preferably, it is 40-250 mass part, More preferably, it is 50-200 mass part. When content of the said component (D) exists in the said range, it is excellent in alkali developability and can form the light shielding film excellent in intensity | strength. In addition, when there is too little content of the said component (D), the intensity | strength and surface smoothness of a light shielding film may fall. On the other hand, when there is too much content of the said component (D), alkali developability may fall or a ground stain, a film | membrane residue, etc. may generate | occur | produce in an unexposed part.

The radiation-sensitive composition for forming a light-shielding film of the present invention includes the component (D) and a monomer having one polymerizable unsaturated bond (hereinafter referred to as “monofunctional monomer”). Can be used in combination.
Examples of the monofunctional monomer include N- (meth) acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε, as well as various monomers exemplified as the monomer for forming the component (B). -Caprolactam, commercially available "M-5600" (trade name, manufactured by Toagosei Co., Ltd.) and the like can be mentioned. These monofunctional monomers may be used alone or in combination of two or more.

  When the monofunctional monomer is used, the amount used is preferably 90% by mass or less, more preferably 50% by mass or less, based on the total of the component (D) and the monofunctional monomer. is there. If it is the said ratio, it is excellent in the intensity | strength and surface smoothness of the light shielding film obtained.

  The component (E) is a photopolymerization initiator, and is a biimidazole compound, a benzoin compound, an acetophenone compound, a benzophenone compound, an α-diketone compound, a polynuclear quinone compound, a xanthone compound, a phosphine compound, Examples include triazine compounds and O-acyloxime compounds. These may be used alone or in combination of two or more.

Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2 '-Bis (2-bromophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4 , 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 '-Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis ( 2-Bromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′- Imidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6) -Tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.
Since the biimidazole compound is excellent in solubility in an organic solvent, the composition containing this compound does not generate foreign matters such as undissolved matter and precipitates, and has high sensitivity and exposure with a small amount of energy. Can sufficiently advance the curing reaction. And since the contrast is high and a curing reaction does not occur in the unexposed area, the film after exposure has a cured area that is insoluble in the developer and an uncured area that is highly soluble in the developer. It is clearly divided into Thereby, it is possible to form a high-definition pattern array in which pixel patterns and black matrix patterns without undercuts are arranged according to a predetermined arrangement.

Examples of the benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and methyl 2-benzoylbenzoate.
Examples of the acetophenone compound include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 4- (2- Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2 -Dimethoxy-1,2-diphenylethane-1-one and the like.

Examples of the benzophenone compounds include 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone.
Examples of the α-diketone compound include diacetyl, dibenzoyl, and methylbenzoylformate.
Examples of the polynuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1,4-naphthoquinone, and the like.
Examples of the xanthone compound include xanthone, thioxanthone, 2-chlorothioxanthone and the like.
Examples of the phosphine compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2 -Yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s- Triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl]- 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n- butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.

  Examples of the O-acyloxime type compound include ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime), ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) Methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

  Content of the said photoinitiator (E) contained in the radiation sensitive composition for light shielding film formation of this invention is 100 mass in total of the said alkali-soluble resin (B) and a polyfunctional monomer (D). The amount is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, and still more preferably 5 to 30 parts by mass with respect to parts. When content of the said component (E) exists in the said range, it is excellent in alkali developability and can form the light shielding film excellent in intensity | strength. In addition, when there is too little content of the said component (E), the intensity | strength and surface smoothness of a light shielding film may fall. On the other hand, when there is too much content of the said component (E), alkali developability may fall or a ground stain, film | membrane residue, etc. may generate | occur | produce in an unexposed part.

  The radiation-sensitive composition for forming a light-shielding film of the present invention contains various additives such as a hydrogen donor, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent as necessary. can do.

The said hydrogen donor is a component normally used together when the said component (E) contains a biimidazole type compound, A sensitivity can further be improved by using this. The “hydrogen donor” is a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
The hydrogen donor is preferably a mercaptan compound defined below, an amine compound defined below, or the like.
The mercaptan-based compound is preferably a compound having an aromatic ring or a heterocyclic ring as a mother nucleus and one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus. Yes, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2,5-dimethylaminopyridine and the like.
In addition, the amine compound preferably has an aromatic ring or a heterocyclic ring as a mother nucleus, and has one or more, preferably 1-3, more preferably 1-2 amino groups bonded directly to the mother nucleus. 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 4-dimethylaminoethyl benzoate, 4- Examples include isoamyl dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
A hydrogen donor having a mercapto group and an amino group can also be used.

  When the radiation sensitive composition for light shielding film formation of this invention contains the said hydrogen donor, the content is 100 mass parts in total of the said alkali-soluble resin (B) and a polyfunctional monomer (D). On the other hand, it is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 25 parts by mass, and still more preferably 1 to 20 parts by mass. When the content of the hydrogen donor is within the above range, it is possible to increase the sensitivity of the coating film formed using the radiation-sensitive composition for forming a light-shielding film of the present invention.

The surfactant may be cationic, anionic, nonionic or amphoteric, and may be used alone or in combination.
Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, and the like. Polyoxyethylene alkyl phenyl ethers of the following: polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid modified polyesters; tertiary amine modified polyurethanes and the like.

  When the radiation sensitive composition for light shielding film formation of this invention contains the said surfactant, the content is 100 mass parts in total of the said alkali-soluble resin (B) and a polyfunctional monomer (D). On the other hand, it is preferably 0.01 to 5 parts by mass, more preferably 0.03 to 4 parts by mass, and still more preferably 0.05 to 3 parts by mass.

  Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl). ) -3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Examples include methoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  When the radiation sensitive composition for light shielding film formation of this invention contains the said adhesion promoter, the content is 100 mass parts in total of the said alkali-soluble resin (B) and a polyfunctional monomer (D). On the other hand, it is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass, and still more preferably 0.5 to 10 parts by mass.

Examples of the antioxidant include 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and the like.
Examples of the ultraviolet absorber include 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like.
Moreover, sodium acrylate etc. are mentioned as said aggregation inhibitor.

  Furthermore, an organic acid or an organic amino compound or the like that can improve the solubility characteristics of the composition in an alkaline developer and further suppress the remaining undissolved material after development can be used.

As the organic acid, any aliphatic carboxylic acid or aromatic carboxylic acid may be used as long as it is a compound having one or more carboxyl groups in the molecule. Moreover, you may combine these.
Aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutar Acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, itaconic acid, citraconic acid And dicarboxylic acids such as maleic acid, fumaric acid, and mesaconic acid; and tricarboxylic acids such as tricarbaric acid, aconitic acid, and camphoric acid.

  Examples of aromatic carboxylic acids include compounds in which a carboxyl group is directly bonded to a phenyl group, compounds in which a carboxyl group is bonded to a phenyl group via a carbon chain, and the like. Benzoic acid, toluic acid, cumic acid, hemelic acid Aromatic monocarboxylic acids such as mesitylene acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, melophanoic acid and pyromellitic acid Phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidene acid, coumaric acid, and umberic acid.

  When the radiation sensitive composition for light shielding film formation of this invention contains the said organic acid, the content becomes like this. Preferably it is 15 mass% or less with respect to the whole composition, More preferably, it is 10 mass% or less. In this case, when there is too much content of the said organic acid, the adhesiveness of a light shielding film may fall.

Moreover, as said organic amino compound, as long as it is a compound which has a 1 or more amino group in a molecule | numerator, you may use any of an aliphatic amine and an aromatic amine. Moreover, you may combine these.
Examples of the aliphatic amine include n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexyl Mono (cyclo) alkylamines such as amine and 4-ethylcyclohexylamine; methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di Isopropylamine, di-n-butylamine, di-isobutylamine, di-sec-butylamine, di-tert-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine, dicyclohexylamine Di (cyclo) alkylamines such as: dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, Tri-isopropylamine, tri-n-butylamine, tri-isobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine, Tri (cyclo) alkylamines such as methylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine; 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4 Mono (cyclo) alkanolamines such as amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino-1-cyclohexanol; diethanolamine, di-n-propanolamine, Di (cyclo) alkanol amines such as di-isopropanolamine, di-n-butanolamine, di-isobutanolamine, di-n-pentanolamine, di-n-hexanolamine, di (4-cyclohexanol) amine Min; triethanolamine, tri-n-propanolamine, tri-isopropanolamine, tri-n-butanolamine, tri-isobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine, tri (4- Tri (cyclo) alkanolamines such as cyclohexanol) amine; 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino- 1,3-butanediol, 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propane Diol, 2-dimethylamino-1,3-propanediol, 2-diethyla Amino (cyclo) alkanediols such as 1,3-propanediol; 1-aminocyclopentanemethanol, 4-aminocyclopentanemethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanemethanol Amino group-containing cycloalkanemethanol such as 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol; β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2- Aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-amino And aminocarboxylic acids such as nocyclohexanecarboxylic acid.

  Examples of the aromatic amine include compounds in which an amino group is directly bonded to a phenyl group, compounds in which an amino group is bonded to a phenyl group via a carbon chain, and the like. Aniline, 2-methylaniline, 3-methylaniline 4-methylaniline, 4-ethylaniline, 4-n-propylaniline, 4-isopropylaniline, 4-n-butylaniline, 4-tert-butylaniline, 1-naphthylamine, 2-naphthylamine, N, N-dimethyl Aniline, N, N-diethylaniline, 4-methyl-N, N-dimethylaniline, 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylaminobenzyl alcohol, 4-diethylaminobenzyl alcohol , 2-aminophenol, 3-aminophe Lumpur, 4-aminophenol, 4-dimethylamino phenol, 4-diethylamino-phenol, and the like.

  When the radiation-sensitive composition for forming a light-shielding film of the present invention contains the organic amino compound, the content thereof is preferably 15% by mass or less, more preferably 10% by mass or less, based on the entire composition. . In this case, when there is too much content of the said organic acid, the adhesiveness of a light shielding film may fall.

  The radiation-sensitive composition for forming a light-shielding film of the present invention is usually a composition in which each of the above components is dissolved or dispersed in an organic solvent. Examples of the organic solvent include alkylene glycol monoalkyl ether, alkylene glycol monoalkyl ether acetate, other ether compounds, ketone compounds, alkyl lactate esters, other ester compounds, aromatic hydrocarbons, amide compounds, and lactam compounds. . These may be used alone or in combination of two or more.

  Examples of the alkylene glycol monoalkyl ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n. -Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n- Butyl ether, dipropylene Glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether and the like.

Examples of the alkylene glycol monoalkyl ether acetate include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and the like. .
Examples of the other ether compounds include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran.
Examples of the ketone compound include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.

Examples of the alkyl lactate include methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, and isobutyl lactate.
Examples of the other ester compounds include ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate , Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n acetate -Butyl, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate , Methyl acetoacetate, acetoacetic acid Chill, ethyl and 2-oxobutanoate, and the like.

Examples of the aromatic hydrocarbon include toluene and xylene.
Examples of the amide compound include N, N-dimethylformamide, N, N-dimethylacetamide and the like.
Examples of the lactone compound include γ-butyrolactone.

  Examples of the organic solvent include propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether from the viewpoints of solubility, dispersibility, coatability, and the like. , Cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, acetic acid n- Butyl, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, Ethyl bottle acid, and the like are preferable.

  The organic solvent is benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, oxalic acid. A high boiling point solvent such as diethyl, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate may be included. These high-boiling solvents can be used alone or in combination of two or more.

  The amount of the organic solvent used is not particularly limited, but the total concentration of each component excluding the organic solvent of the composition is usually 5 to 50% by mass, from the viewpoint of the coating property and stability of the composition. Preferably, it is selected to be 10 to 40% by mass.

  The manufacturing method of the radiation sensitive composition for light shielding film formation of this invention is not specifically limited, For example, in organic solvent, predetermined amount of component (A), (B), (C), (D) and It can be set as the method etc. which mix (E) etc. collectively or by dividing and mixing. Examples of the mixing apparatus include two rolls, three rolls, a ball mill, a tron mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single screw extruder, and a twin screw extruder. After mixing, if necessary, it may be filtered with a filter.

The radiation-sensitive composition for forming a light-shielding film of the present invention is a composition used for forming a light-shielding film on the periphery of an effective pixel region in a solid-state imaging device. A film having excellent properties and resolution can be formed, and the insulating properties of a film (light-shielding film) obtained through exposure, development, and the like are also excellent.
The light-shielding film for a solid-state imaging device of the present invention is characterized in that the light-sensitive composition for forming a light-shielding film of the present invention is disposed on the periphery of the effective pixel region.
Furthermore, the solid-state image sensor of the present invention is characterized by including the light-shielding film for the solid-state image sensor of the present invention.

Hereinafter, a light-shielding film for a solid-state image sensor of the present invention (hereinafter simply referred to as “light-shielding film”), a method for forming the same, and a solid-state image sensor of the present invention including the same will be described.
The light shielding film for solid-state image sensors of this invention and the solid-state image sensor of this invention are illustrated (refer FIGS. 1-4).

  A solid-state imaging device 1 shown in FIG. 1 is made of a silicon wafer, glass, or the like, and includes a substrate 11 having a recess opening upward in the drawing, a photoelectric conversion unit 12 disposed at the bottom of the recess of the substrate 11, and the recess. Refractive index portion (high or low) 13 formed to fill, color filters 14B, 14G and 14R formed on the surface of this refractive index portion, and region A (effective pixel region) occupied by these color filters ), The planarizing layer 16 formed on the surfaces of the color filters 14B, 14G, and 14R, and the surface of the planarizing layer 16 on the color filters 14B, 14G, and 14R. A condensing microlens 17 is provided above these according to the position.

Elements such as the photoelectric conversion unit 12 in the concave portion of the substrate 11 and the size thereof, and further, elements in the peripheral part can be appropriately changed. For example, the embodiment shown in FIGS.
1 to 3, the planarization layer 16 may be formed on the surface of the light shielding film 15 (not shown).
Further, the solid-state imaging device 1 in which the planarization layer 16 is omitted in FIG. 1 can be used (see FIG. 4).
In FIG. 1 to FIG. 4, internal circuits and the like are omitted.

1 to 4, the light shielding film 15 is formed on the surface of the substrate 11, but is not limited thereto. For example, the refractive index portion (high or low) 13 is widely formed on the surface of the substrate 11. If it is, it may be arranged on the surface of the refractive index portion (high or low) 13 (not shown).
In addition, the photoelectric conversion unit 12 is not necessarily arranged in the concave portion of the substrate 11 but may be arranged on a flat surface. In this case, a boundary film or the like is disposed between the color filter 14 and the light shielding film 15 so that light does not enter the photoelectric conversion unit 12 below the color filter (not shown).

  The maximum side of each color rectangular unit pixel of the color filter 14 corresponding to the photoelectric conversion unit 12 on the upper side of the photoelectric conversion unit 12 is generally 1.5 to 20 μm. From the viewpoint of miniaturization of a solid-state imaging device including a solid-state imaging device and high-speed operation of the solid-state imaging device, it is preferably 5 μm or less, more preferably 4 μm or less, and further preferably 3 μm or less.

  The light shielding film 15 is usually formed by applying the radiation sensitive composition for forming a light shielding film of the present invention to a light shielding film forming substrate (not shown) having a color filter 14 and then performing prebaking. The organic solvent is evaporated to form a film. Next, the film is exposed through a photomask with a predetermined pattern designed to expose at least the color filter 14 after development. And it develops using an alkali developing solution, and the unexposed part of a film is dissolved and removed. Then, the light shielding film 15 for solid-state image sensors of this invention can be obtained by performing post-baking as needed.

  When applying the radiation-sensitive composition for forming a light-shielding film of the present invention, a known coating method such as spin coating, cast coating, roll coating or the like can be applied. The thickness of the coating film is not particularly limited.

  Thereafter, the temperature at which the above-mentioned coating film is pre-baked is appropriately selected depending on the components of the coating film and the like, but is usually selected from the range of 70 ° C to 130 ° C, preferably from 80 ° C to 120 ° C. . This heat treatment may be performed at a constant temperature in the above range, or may be performed by combining temperature increase and temperature decrease.

Next, the pre-baked film is exposed using radiation such as light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays. The wavelength of the radiation is preferably in the range of 190 to 450 nm. The exposure energy amount of the radiation is preferably 10~10,000J / ^{m 2.}

Thereafter, the alkali developer used for developing the exposed portion of the film includes sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, and dimethyl. Ethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, 1,5-diazabicyclo- [4.3.0 An aqueous solution of -5-nonene is preferable. In addition, this aqueous solution may be one in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like is added.
Examples of the development method include a shower development method, a spray development method, a dip (immersion) development method, and a paddle (liquid accumulation) development method. The development time is usually 5 to 300 seconds at room temperature (22 ° C. to 28 ° C.).
After alkali development, washing and drying are usually performed. Examples of the drying method include heat drying using a hot plate, an oven, etc .; air drying using an air gun or the like.

  The patterned film (light-shielding film) obtained as described above can be post-baked as necessary to obtain a light-shielding film having excellent adhesion. The temperature at which the patterned film is post-baked is appropriately selected depending on the constituents of the patterned film, etc., but is usually selected from the range of 150 ° C. to 250 ° C., preferably from 170 ° C. to 230 ° C. It is.

The light shielding film may be either a single layer or a multilayer. Moreover, the said light shielding film is exhibiting black because the formation composition contains the black pigment.
The thickness of the light shielding film is preferably 3 μm or less, more preferably 0.5 to 2.5 μm, and still more preferably 0.8 to 2.0 μm, from the viewpoint of light shielding properties and adhesion. If the thickness of the light shielding film is too thin, light from the outside of the solid-state imaging device including the solid-state imaging device may leak from the lower surface side, and the performance of the solid-state imaging device may deteriorate. On the other hand, if the thickness of the light shielding film exceeds 3 μm, wrinkles due to curing shrinkage may occur.

  The light-shielding film is not only at normal temperature (0 ° C. to 30 ° C.) and humidity (10 to 100%), but also from low temperature to high temperature and high humidity (temperature −50 ° C. to 230 ° C. and humidity 10 to 130%). Even under conditions, the solid-state image pickup device and the solid-state image pickup device including the light-shielding film of the present invention have excellent light-shielding properties for light having a wavelength of 400 to 1,600 nm and adhesion to the insulating portion. Excellent.

  The light shielding property of the light shielding film is such that, for example, when a film having a thickness of 1.4 μm is irradiated with light having a wavelength of 1,200 nm, the transmittance is preferably 1.5% or less, more preferably 1.3%. % Or less, and has excellent light shielding properties.

  The light shielding film may include a protective film on the surface thereof. In that case, an acrylic resin composition, an epoxy resin composition, a polyimide resin composition, or the like can be used as the protective film forming material.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.

1. 1. Raw material component of radiation-sensitive composition for forming light shielding film 1-1. Black pigment (A)
Carbon black was used.
1-2. Modified acrylic block copolymer (B)
“DISPERBYK-2001” (trade name) manufactured by Big Chemie Japan was used.

1-3. Alkali-soluble resin (C)
Alkali-soluble resins C1 and C2 obtained by the following method were used.
(1) Alkali-soluble resin C1
In a flask equipped with a condenser and a stirrer, 15.0 g of methacrylic acid, 30.0 g of acenaphthylene, 40.0 g of benzyl methacrylate, 10.0 g of hydroxyethyl methacrylate and 5.0 g of ω-carboxypolycaprolactone monoacrylate were mixed with propylene glycol monomethyl. Dissolved in 220 g of ether acetate. Next, 4.0 g of 2,2′-azobisisobutyronitrile and 6.0 g of α-methylstyrene dimer were added, and the inside of the flask was purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring. And the polymerization solution which contains 33 mass% of alkali-soluble resin C1 was obtained by superposing | polymerizing for 5 hours, hold | maintaining this temperature. This alkali-soluble resin C1 had a polystyrene-reduced weight average molecular weight (Mw) by GPC of 13,000.

(2) Alkali-soluble resin C2
In a flask equipped with a condenser and a stirrer, 25.0 g of methacrylic acid, 30.0 g of N-phenylmaleimide, 18.0 g of styrene, 15.0 g of benzyl methacrylate and 12.0 g of 2-acryloyloxyoxyethyl succinic acid, Dissolved in 200 g of cyclohexanone. Next, 1.0 g of 2,2′-azobisisobutyronitrile and 2.5 g of α-methylstyrene dimer were charged, and the inside of the flask was purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring. And the polymerization solution which contains 33 mass% of alkali-soluble resin C2 was obtained by superposing | polymerizing for 5 hours, hold | maintaining this temperature. The weight average molecular weight (Mw) in terms of polystyrene by GPC of this alkali-soluble resin C2 was 22,000.

1-4. Multifunctional monomer (D)
Dipentaerythritol hexaacrylate (trade name “MAX3510”, manufactured by Toagosei Co., Ltd.) was used.
1-5. Photopolymerization initiator (E)
(1) E1
2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (2) E2
2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (3) E3
4,4′-bis (diethylamino) benzophenone (4) E4
Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime)

1-6. Solvent (F)
(1) F1
Propylene glycol monomethyl ether acetate (2) F2
3-methoxybutyl acetate (3) F3
Cyclohexanone 1-7. Additive (G)
(1) Hydrogen donor G1
2-mercaptobenzothiazole (2) surfactant G2
3-Glycidoxypropyltrimethoxysilane (3) Surfactant G3
Neos "Factent FRX-218" (trade name) was used.
(4) Surfactant G4
AGATHOS International B. “W005” (trade name) manufactured by V Company was used.
(5) Surfactant G5
DIC's “MegaFuck F475” (trade name) was used.

2. Production and Evaluation of Radiation Sensitive Composition for Formation of Light Shielding Film In producing the radiation sensitive composition for formation of light shielding film, a black pigment dispersion was prepared in advance by the following method.
<Preparation of black pigment dispersion>
Using a bead mill, 20.0 parts by mass of a black pigment, 4.0 parts by mass of a modified acrylic block copolymer, and 3-methoxybutyl acetate as a solvent were mixed so as to have a solid content concentration of 86% by mass. A black pigment dispersion was prepared.

Example 1
100 parts by weight of a black pigment dispersion, 19 parts by weight of a polymerization solution (solid content concentration 33% by weight) containing an alkali-soluble resin C1, 10.0 parts by weight of a polyfunctional monomer, and a photopolymerization initiator (E1) 2.6 parts by mass, 2.0 parts by mass of photopolymerization initiator (E2), 0.7 parts by mass of photopolymerization initiator (E3), 1.0 part by mass of additive (G1), and additive ( G2) 0.7 parts by mass, additive (G3) 0.02 parts by mass, additive (G4) 0.01 parts by mass, solvent (F1) 10.0 parts by mass, and solvent (F3) 17. 0 part by mass was mixed to obtain a radiation sensitive composition for forming a light shielding film. Table 1 shows constituent components and ratios of the radiation-sensitive composition for forming a light-shielding film.

About the obtained radiation sensitive composition for light shielding film formation, the following item was evaluated. The results are shown in Table 1.
[1] Residue and pattern size After the radiation-sensitive composition for forming a light-shielding film was applied to a silicon wafer substrate using a spin coater, it was pre-baked on a 90 ° C. hot plate for 2 minutes and 30 seconds to obtain a film thickness. A 1.7 μm film was formed. Next, the substrate is cooled to room temperature, and each wavelength of 365 nm, 405 nm, and 436 nm is applied to the coating film through a photomask having a width of 50 μm using an exposure apparatus (trade name “Mask Aligner MA200e”, manufactured by SUSS). Exposed ultraviolet light was exposed. The exposure amount at this time was 500 J / m ² .
Thereafter, the substrate was shower-developed for 1 minute using a 0.05 mass% tetramethylammonium hydroxide aqueous solution containing a polyoxyethylene surfactant at 23 ° C. And it wash | cleaned and air-dried using the ultrapure water. Next, post baking was performed on a hot plate at 180 ° C. for 5 minutes to form a patterned film on the substrate. The obtained patterned film was observed with an electron microscope, and whether or not a pixel pattern residue was observed was determined according to the following criteria. At this time, the minimum pattern size (μm) that remained without peeling off the entire pattern was measured.
○: No residue is observed.
X: There are many residues.

[2] Transmittance After the radiation-sensitive composition for forming a light-shielding film was applied to a glass substrate using a spin coater, it was pre-baked on a hot plate at 90 ° C. for 2 minutes and 30 seconds to obtain a film thickness of 1.5 μm. Was formed. Next, the substrate was cooled to room temperature, and ultraviolet rays including wavelengths of 365 nm, 405 nm, and 436 nm were exposed on the entire surface of the coating film using an exposure apparatus (trade name “Mask Aligner MA200e”, manufactured by SUSS). The exposure amount at this time was 500 J / m ² .
Thereafter, it was post-baked on a 180 ° C. hot plate for 5 minutes to form a film (thickness: 1.4 μm).
Transmittance was measured at a temperature of 23 ° C. and a wavelength range using a spectrophotometer (model “V7300”, manufactured by JASCO Corporation) for the blank film and the film subjected to the following various conditions (a) to (c). The measurement was performed at 400 to 1,300 nm, and the transmittance at 1,200 nm was evaluated.
(A) A film after the substrate with a film is left for 168 hours under conditions of a temperature of 85 ° C. and a humidity of 85% using a constant temperature and humidity test apparatus (model “PSL-2KPH”, manufactured by Espec).
(B) A film after the substrate with a film is left for 168 hours under conditions of a temperature of 110 ° C. and a humidity of 100% using a highly accelerated life test apparatus (model “TPC-212”, manufactured by Espec Corp.).
(C) A film after the film-coated substrate is left on the hot plate in the atmosphere at 260 ° C. for 1 hour.

[3] Adhesiveness After applying the radiation-sensitive composition for forming a light-shielding film to a silicon wafer substrate and a glass substrate using a spin coater, prebaking was performed on a hot plate at 90 ° C. for 2 minutes and 30 seconds to obtain a film thickness. A 1.3 μm film was formed. Then, using an exposure apparatus (trade name “Mask Aligner MA200e”, manufactured by SUSS), the entire surface of the coating film was exposed to ultraviolet rays including wavelengths of 365 nm, 405 nm, and 436 nm. The exposure amount at this time was 500 J / m ² .
Thereafter, it was post-baked on a hot plate at 180 ° C. for 5 minutes to form a film to obtain a light-shielding film.
Adhesion is to create 100 1 mm square grids using a cutter and cutter guide conforming to JIS K5400 for the blank film and the light shielding film subjected to the following condition (d). Confirmed (cross cut test). The grids remaining after peeling the tape were counted.
(D) A light-shielding film after leaving the substrate with a light-shielding film to stand for 168 hours under conditions of a temperature of 110 ° C. and a humidity of 100% using a highly accelerated life test apparatus (model “TPC-212”, manufactured by Espec Corp.).

Examples 2-4
Composition shown in Table 1 using a black pigment dispersion, a polymerization solution containing the alkali-soluble resin C1 or the alkali-soluble resin C2, a polyfunctional monomer, a photopolymerization initiator, a solvent, and an additive. Except for the above, a radiation-sensitive composition for forming a light-shielding film was obtained in the same manner as in Example 1. And evaluation similar to Example 1 was performed and the result was written together in Table 1.

  The radiation-sensitive composition for forming a light-shielding film of the present invention is a light-shielding film for a solid-state imaging device disposed in an electronic device such as a digital camera, a video camera, an in-vehicle camera, a personal computer having a photographing function, a mobile phone, or an electronic notebook. It is suitable for.

It is a schematic sectional drawing which shows an example of the light shielding film and solid-state image sensor of this invention. It is a schematic sectional drawing which shows the other example of the light shielding film of this invention, and a solid-state image sensor. It is a schematic sectional drawing which shows the other example of the light shielding film of this invention, and a solid-state image sensor. It is a schematic sectional drawing which shows the other example of the light shielding film of this invention, and a solid-state image sensor.

Explanation of symbols

1: solid-state imaging device 11: substrate 12: photoelectric conversion unit 13: refractive index unit 14 (14G, 14B and 14R): color filter 15: light shielding film 16: planarization layer 17: microlens A: effective pixel region (imaging unit) )

Claims (6)

A radiation-sensitive composition for forming a light-shielding film used to form a light-shielding film on the periphery of an effective pixel region in a solid-state imaging device,
(A) a black pigment,
(B) a modified acrylic block copolymer having an acid value of 15 to 40 mg KOH / g and an amine value of 25 to 40 mg KOH / g,
(C) an alkali-soluble resin having a repeating structural unit derived from acenaphthylene or N-phenylmaleimide;
(D) a polyfunctional monomer, and
(E) a photopolymerization initiator,
And contain,
The content of the (A) black pigment is 70 to 300 parts by mass with respect to 100 parts by mass in total of the (C) alkali-soluble resin and the (D) polyfunctional monomer. A radiation-sensitive composition for forming a light-shielding film.   The radiation-sensitive composition for forming a light-shielding film according to claim 1, wherein the black pigment is carbon black and / or titanium black.   A light-shielding film for a solid-state imaging device, characterized in that the radiation-sensitive composition for forming a light-shielding film according to claim 1 or 2 is disposed on the periphery of the effective pixel region.   The light shielding film for a solid-state imaging device according to claim 3, wherein the thickness of the light shielding film is 3 μm or less.   5. A solid-state imaging device, wherein the light-shielding film for a solid-state imaging device according to claim 3 or 4 is disposed on a periphery of the effective pixel region.   The solid-state imaging device according to claim 5, wherein the maximum side of the rectangular unit pixel of the color filter corresponding to the photoelectric conversion unit included in the solid-state imaging device is 5 μm or less.

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