JP2007249190A - Photocurable composition, antireflection film using the same, and solid imaging element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable composition having good curing performance and excellent adhesion to a substrate, an antireflection film which is formed using the photocurable composition, has excellent adhesion to a substrate, suppresses production of a false signal due to stray light, and ensures few color defects, and a solid imaging element with the antireflection film. <P>SOLUTION: The photocurable composition contains a colorant, a photopolymerizable compound, a photoinitiator and an alkali-soluble resin, wherein the photopolymerizable compound contains any one of at least a bisphenol compound and an isocyanuric ring-containing compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photocurable composition used for a solid-state imaging device such as a CCD or CMOS, an antireflection film using the same, and a solid-state imaging device.

In a solid-state imaging device, when forming a color filter or a microlens in a photolithography process, there is a problem that a pattern shape is deteriorated by reflected light from an aluminum light-shielding film or wiring formed in a lower layer. In terms of the performance of the solid-state image sensor, the reflected light from the aluminum light-shielding film / wiring is further reflected at the interface of the color filter / flattening film, etc., and is incident on the photodiode as stray light to generate a false signal. It has become.
In order to suppress such a phenomenon, a black pattern that absorbs light is formed on an aluminum light-shielding film / wiring.
Conventionally, a dyeing method in which a pattern is formed and then dyed with a black dye to form an antireflection film has been disclosed (for example, Patent Document 1). However, it is difficult to reduce the thickness by this method, and the aperture ratio of the pixel is lowered. Moreover, heat resistance and light resistance are inferior by using a dye.
In addition, a method of forming a nitride film with low reflectance on an aluminum light shielding film is disclosed (for example, Patent Document 2). However, since the nitride film has a limited wavelength to be absorbed, it cannot absorb from the visible light to the infrared light region, and has no antireflection performance for light in some wavelength bands. Therefore, it can be used to prevent halation when forming color filters and microlenses to be formed later, and to make the pattern shape rectangular, but it is used to prevent the generation of false signals due to stray light. I could not. Moreover, the process of forming and patterning the nitride film is extremely complicated. Especially when the nitride film is formed without interposing the interlayer film, a local battery is formed between the aluminum and nitride films during etching, and the aluminum is corroded. As a result, the edge shape deteriorated and chipped, causing defects.

On the other hand, the method for improving the peelability of a film transfer method color filter using the photosensitive composition containing a tris isocyanuric acid compound is disclosed (for example, refer patent document 3). However, there is only a disclosure example of a color filter for a liquid crystal display, and there is no disclosure of the above reflective film for a solid-state imaging device, and the peelability from the cover film during the production of the color filter by the film transfer method is a problem. ing.
Also disclosed is a method for improving the storage stability and curability of a color filter using a dark photosensitive resin composition containing isocyanuric acid ethylene oxide-modified tri (meth) acrylate as a photopolymerizable compound (for example, (See Patent Document 4). However, it is an invention relating to a color filter by a dyeing method and an invention for improving the storage stability of the photosensitive resin composition.
Further, it is described that a bisphenol-based compound can be used for a photosensitive colored image forming material used for producing a color filter (see, for example, Patent Document 5). However, the main subject is the invention of the developer, and only an example of the monomer used for the colored image forming material is disclosed.
JP-A-3-276678 Japanese Patent Application Laid-Open No. 6-0342896 JP 10-333330 A JP-A-8-062841 Japanese Patent Laid-Open No. 10-239859

Since carbon black used as the colorant of the present invention has a light absorption characteristic for wavelengths from the ultraviolet light to the infrared light region, when used as a colorant for the photosensitive composition for forming an antireflection film, It can have an antireflection effect for wavelengths up to the infrared region. However, with the trend toward downsizing and higher resolution of solid-state imaging devices, etc., when the line width for forming the antireflection film becomes less than 1.5 μm, it is regulated by the flow of developer / rinse liquid in the development / rinse process. It has been found that a phenomenon in which a general distortion occurs occurs.
In view of the above, an object of the present invention is to solve the above conventional problems.
That is, the present invention provides a photocurable composition having good curing performance and excellent adhesion to the substrate, and also having excellent adhesion to the substrate formed using the photocurable composition. An object of the present invention is to provide an antireflection film that reduces the generation of false signals due to stray light and has few color defects.
It is another object of the present invention to provide a solid-state imaging device having the antireflection film that has excellent adhesion to a base, reduces generation of false signals due to stray light, and has few color defects.

In view of the above circumstances, the present inventors conducted extensive research and found that a photocurable composition containing a bisphenol compound or isocyanurate ring-containing compound having a specific chemical structure as a photopolymerizable compound was dispersed in a black colorant. The present invention was completed by finding that the above-mentioned problems can be solved by using it in the photocurable composition.
In other words, a monomer having a (meth) acryloyl group having a bisphenol skeleton and / or a monomer having a (meth) acryloyl group having an isocyanuric skeleton as a curing component, which has good curing performance and excellent adhesion to the base, is used. Thus, it was found that the occurrence of distortion can be suppressed, and a photocurable composition that does not generate distortion was completed.
At this time, carbon black is preferable as the colorant. Since carbon black is a stable substance, it does not decompose like a dye after pattern formation, has excellent heat resistance and light resistance, and because carbon has a filler effect, it does not deform due to heat, so it is easy to process. Excellent.
The present invention is achieved by the following means.

<1> In a photocurable composition containing a colorant, a photopolymerizable compound, a photopolymerization initiator, and an alkali-soluble resin, the photopolymerizable compound contains at least one of a bisphenol compound and an isocyanuric ring-containing compound. A photocurable composition comprising.
<2> The photocurable composition according to <1>, wherein the colorant includes carbon black having an average primary particle size of 10 nm or more and 30 nm or less.

<3> The photocurable composition according to the above <1> or <2>, wherein the colorant contains a plurality of colors of organic pigments.
<4> The photocurable composition according to any one of <1> to <3>, wherein the photopolymerizable compound includes at least one of the following general formulas (I) and (II).

(In General Formula (I), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ³ and R ⁴ each independently represent an ethylene group or a propylene group, m , N each independently represents an integer of 1 or more and m + n represents an integer of 3 to 40 (m + n is preferably an integer of 4 to 30), and A ¹ and A ² each independently represents an acryloyl group or an allyl group. .)

(In the general formula (II), R ¹ , R ² and R ³ each independently represents an ethylene group or a propylene group, and a, b and c each independently represents an integer of 0 to 6. m, n, l Are each an integer, and m + n + 1 represents an integer of 0 to 18, and A ¹ , A ² and A ³ each independently represents an acryloyl group or an allyl group.)

<5> An antireflection film having a width of 1.5 μm or less formed on the substrate after using the photocurable composition according to any one of <1> to <4>.
<6> An antireflection film having a thickness of 1.0 μm or less formed on a substrate using the photocurable composition according to any one of <1> to <4>.

<7> A solid-state imaging device having the antireflection film according to <5> or <6>.

That is, according to the present invention, it is possible to provide a photocurable composition having good curing performance and excellent adhesion to the base.
Further, according to the present invention, it is possible to provide an antireflection film which is formed using the photocurable composition and has excellent adhesion to the base, generation of false signals due to stray light is reduced, and there are few color defects.
Another object of the present invention is to provide a solid-state imaging device having the antireflection film that has excellent adhesion to the ground, reduces the generation of false signals due to stray light, and has few color defects.

The photocurable composition of the present invention contains a colorant, a photopolymerizable compound, a photopolymerization initiator, and an alkali-soluble resin, and the photopolymerizable compound is at least one of a bisphenol compound and an isocyanuric ring-containing compound. including.
When the photocurable composition contains at least one of a bisphenol-based compound and an isocyanuric ring-containing compound as the photopolymerizable compound, the composition has excellent curing performance and excellent adhesion to the base. Can do.
Hereinafter, the present invention will be described in detail.

≪Photocurable composition≫
The photocurable composition of the present invention contains a colorant, a photopolymerizable compound, a photopolymerization initiator, and an alkali-soluble resin. As the photopolymerizable compound, at least one of a bisphenol compound and an isocyanuric ring-containing compound is used. It is a composition containing. Moreover, generally, a solvent can be used and other components can be added as needed.

-Photopolymerizable compound-
As described above, the photopolymerizable compound used in the composition of the present invention contains at least one of a bisphenol compound and an isocyanuric ring-containing compound.

(Bisphenol compounds)
The bisphenol compound is not particularly limited as long as it is photopolymerizable, and a conventionally known compound can be used.
Among these, a compound represented by the following general formula (I) is preferable.

In general formula (I), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ³ and R ⁴ each independently represents an ethylene group or a propylene group, m, n is an integer of 1 or more and m + n represents an integer of 3 to 40, preferably m + n is an integer of 4 to 30. A ¹ and A ² each independently represents an acryloyl group or an allyl group.

Examples of the hydrocarbon group having 1 to 8 carbon atoms represented by R ¹ and R ² include aliphatic hydrocarbon groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; a phenyl group and the like And an alicyclic hydrocarbon group such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a 1-cyclohexenyl group.
The hydrocarbon group may be substituted or unsubstituted.

R ³ and R ⁴ each independently represents an ethylene group or a propylene group, and may be the same or different.
The ethylene group and propylene group may be substituted or unsubstituted. Examples of the substituent include the substituents of the hydrocarbon group represented by R ¹ and R ² .

  Examples of the bisphenol compounds include NK ester ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-13, and A manufactured by Shin-Nakamura Chemical Co., Ltd. -BPE-20: New Frontier BPE-10, BPE-20, BPP-4, BPEM-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; Aronix M-208, M- manufactured by Toagosei Co., Ltd. 210, M-211B; Kyoeisha Chemical Co., Ltd. light ester BP-4EM, BP-6EM, BP-4PA, BP-10EA, and the like.

(Isocyanuric ring-containing compound)
The isocyanuric ring-containing compound is not particularly limited as long as it is photopolymerizable, and conventionally known compounds can be used.
Among the above, a compound represented by the following general formula (II) is preferable.

In the general formula ^{(II), R 1, R} 2, R 3 each independently represents an ethylene group or a propylene group, a, b, c are each independently represent an integer of 0-6. m, n, l is an integer, respectively, and, m + n + l represents an integer of ^{0~18, A 1, A 2,} A 3 each independently represents an acryloyl group or an allyl group.

The ethylene group or propylene group represented by R ¹ , R ² , or R ³ may have a substituent or may be unsubstituted.
Examples of the substituent include substituents of hydrocarbon groups represented by R ¹ and R ² in the general formula (I).

A ¹ , A ² and A ³ each independently represents an acryloyl group or an allyl group, and the acryloyl group or allyl group may be substituted or unsubstituted. Examples of the substituent include substituents of hydrocarbon groups represented by R ¹ and R ² in the general formula (I).

  Examples of the isocyanuric ring-containing compound include tri- (acryloyloxyethyl) -isocyanurate (trade name: Aronix M315 manufactured by Toagosei Co., Ltd., NK ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., Hitachi Chemical FA-731A manufactured by Daiichi Kogyo Seiyaku Co., Ltd., New Frontier TEICA manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), triallyl isocyanurate (trade name: TAIC manufactured by Nippon Kasei Co., Ltd., TAIC manufactured by Degussa Co., Ltd.) Is mentioned. Furthermore, (acryloyloxyethoxyethyl) -di- (acryloyloxyethyl) -isocyanurate, di- (acryloyloxyethoxyethyl) with a chain extended with ethylene oxide or propylene oxide between the side chain and the isocyanurate ring -(Acryloyloxyethyl) -isocyanurate, tri- (acryloyloxyethoxyethyl) -isocyanurate or the like, or a compound obtained by further increasing the number of additions of ethylene oxide and propylene oxide (maximum is general formula (ii) 21) in total of carbon number including abc can also be used. A compound obtained by chain-extending triallyl isocyanurate with ethylene oxide or the like can also be used.

Moreover, as a photopolymerizable compound in this invention, a general polymerizable monomer can be used in the range which does not impair the effect of this invention.
The polymerizable monomer has at least one addition-polymerizable ethylene group. A compound having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure is preferable, and a tetrafunctional or higher acrylate compound is more preferable.

  Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meta ) Monofunctional acrylates and methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, Poly (meth) of pentaerythritol or dipentaerythritol after addition of ethylene oxide or propylene oxide to polyfunctional alcohols such as ly (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane Acrylates, urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, described in JP-B-49-43191 and JP-B-52-30490 To mention That. Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be used.

  Further, a compound obtained by adding ethylene oxide or propylene oxide to the polyfunctional alcohol and then (meth) acrylated is described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. These can also be used as photosensitive polymerization components.

Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and a structure in which these acryloyl groups are interposed via ethylene glycol or propylene glycol residues are preferable. These oligomer types are also used. These photosensitive polymerization components can be used alone or in combination of two or more.
The content of the photosensitive polymerization component in the photocurable composition is preferably 0.1 to 80% by mass, more preferably 1 to 60% by mass, particularly preferably 5 to 5%, based on the total solid content of the composition. 50% by mass. If the amount of the photosensitive polymerization component used is too small or more than the above range, it is not preferable because curing is insufficient.

<Colorant>
The colorant that can be used in the present invention is not particularly limited, and various conventionally known dyes and pigments can be used singly or in combination.
From the viewpoint of using the photocurable composition of the present invention in an antireflection film described later that requires a small amount and a high optical density, the colorant is black. Hereinafter, the black colorant will be described.

As the black colorant that can be used in the present invention, various known black pigments and black dyes can be used. In particular, from the viewpoint of realizing a high optical density in a small amount, carbon black, titanium black, oxidation Titanium, iron oxide, manganese oxide, graphite, and the like are preferable. Among them, at least one of carbon black and titanium black is preferably included, and carbon black is particularly preferable.
The black colorant may be used alone or in combination of two or more.

The colorant in the present invention preferably contains a plurality of colors of organic pigments from the viewpoint of producing an antireflection film described later.
When used as a photocurable composition for an antireflection film described later, it is preferably used together with the black colorant. By using a combination of organic pigments of a plurality of colors, the optical density of the photocurable composition can be further increased, which is preferable from the viewpoint that jet black can be obtained.
The organic pigments having a plurality of colors are not particularly limited, and various black pigments made by mixing various R, G, B, C, M, and Y known pigments can be used.

The average primary particle size (average primary particle size) of the colorant is preferably small from the viewpoint of preventing the occurrence of protrusions on the surface of the formed image pattern and improving the production efficiency. For example, it is preferable that the average primary particle diameter is small in order to prevent protrusions from being generated in the antireflection film pattern and to produce a solid-state imaging device from the viewpoint of influence on the yield.
The effect of the present invention, prevention of protrusions on the surface of the formed image pattern, in particular, generation of false signals due to stray light is reduced, and the rectangular shape of the image pattern of the antireflection film is improved, and the edges of the rectangle In order to prevent protrusions from being generated in the portion, it is preferably as small as possible, and the average primary particle diameter of the colorant is preferably 30 nm or less, more preferably 10 nm or more and 30 nm or less. Among these, the average primary particle size (particle size) is more preferably 5 to 25 nm, particularly preferably 5 to 20 nm, and most preferably 5 to 15 nm.

The content of the colorant in the total solid content of the photocurable composition of the present invention is not particularly limited, but is preferably as high as possible in order to obtain a high optical density with a thin film. % By mass is preferred, 3-70% by mass is more preferred, and 5-50% by mass is particularly preferred.
If the amount of the colorant is too small, it is necessary to increase the film thickness in order to obtain a high optical density. If the amount of the colorant is too large, the photocuring does not proceed sufficiently and the strength as a film is reduced, or development is performed during alkali development. The latitude tends to narrow.

  As a mass ratio when a plurality of colorants are used in combination and carbon black is used as a main component, the mass ratio between the colorant used in combination with carbon black is preferably in the range of 95: 5 to 60:40, and 95: 5 -70: 30 are more preferable, and 90: 10-80: 20 are still more preferable. The mass of the colorant used in combination is the total mass thereof. By setting the mass ratio of the colorant used in combination with the carbon black in the range of 95: 5 to 60:40, there is a tendency that a stable coating film having no dispersion and no unevenness can be produced.

  Examples of the carbon black in the present invention include carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850 manufactured by Mitsubishi Chemical Corporation. , MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Da Diamond Black N339, Diamond Black SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LP. Carbon black thermax N990, N991, N907, N908, N990, N991, N908 made by Cancarb. Carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa's carbon black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2, ColorBlack Fw1, ColorBlack 170, BlackBlack, BlackBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, PrintexU, PrintexV, Printex140U, Printex140 And the like can be given.

  The carbon black in the present invention is not necessarily insulative, but those having insulative properties can also be used. The carbon black having an insulating property is a carbon black exhibiting an insulating property when the volume resistance as a powder is measured by the following method. For example, an organic substance is adsorbed, coated, or coated on the surface of the carbon black particles. It means having an organic compound on the surface of carbon black particles, such as chemically bonded (grafted).

Carbon black is dispersed in propylene glycol monomethyl ether acetate so that benzyl methacrylate and methacrylic acid have a molar ratio of 70:30 copolymer (mass average molecular weight 30,000) and 20:80 mass ratio. After preparing and coating on 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, the coating film is further heated in a hot plate at 220 ° C. for about 5 minutes. The volume resistance value is measured under an environment of 23 ° C. and 65% relative humidity by applying with a high resistivity meter manufactured by Mitsubishi Chemical Co., Ltd. according to JISK6911 and Hirestar UP (MCP-HT450). Carbon black having a volume resistance value of 10 ⁵ Ω · cm or more, more preferably 10 ⁶ Ω · cm or more, and particularly preferably 10 ⁷ Ω · cm or more is preferable.

Examples of carbon black include, for example, JP-A-11-60988, JP-A-11-60989, JP-A-10-330634, JP-A-11-80583, JP-A-11-80584, and JP-A-9. The resin-coated carbon black disclosed in JP-A-124969 and JP-A-9-95625 can be used.
In particular, the compound represented by the general formula (I) or (II) in the present invention has an advantage that the relative permittivity is small and the influence on the electric signal can be reduced. In particular, since the compound represented by the general formula (II) has a small relative dielectric constant, it is effective when combined with insulating carbon black.

  The photocurable composition of the present invention can be used as a photocurable composition for a color filter. When used as a photocurable composition for the color filter, by containing a plurality of colors of organic pigments, an optical effect substantially equivalent to that of a black colorant, that is, a coating film with low reflectance is formed. Can do it.

-Alkali-soluble resin-
The alkali-soluble resin used in the present invention is not particularly limited as long as it is alkali-soluble.
In the present invention, conventionally known alkali-soluble resins can be used. (I) Maleic anhydride (MAA), methacrylic acid (MA), isobutyl methacrylate (IBMA), acrylic acid (AA), and fumaric acid (Ii) at least one acid component monomer selected from (FA), (ii) (meth) acrylic ester monomers such as alkyl polyoxyethylene (meth) acrylate, benzyl (meth) acrylate, and alkyl (meth) acrylate, and ( iii) It is preferable from an appropriate viewpoint with respect to alkali development to contain an acrylic copolymer with at least one monomer among polymerizable monomers such as styrene.

  The molar content of the acid component monomer in the alkali-soluble resin is 5 to 50 mol%, preferably 10 to 40 mol%.

  Moreover, 1-60 mass% is preferable, as for content of alkali-soluble resin in the composition of this invention, 3-50 mass% is more preferable, and 5-40 mass% is especially preferable. If the content of the alkali-soluble resin is less than 1% by mass, the progress of development is delayed, which may increase the production cost. On the other hand, if it exceeds 60% by mass, a good pattern profile may not be obtained.

In the composition of the present invention, other alkali-soluble resins can be used in combination with the above-mentioned acrylic copolymer as the alkali-soluble resin. The alkali-soluble resin is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution.
Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer as described in JP-A Nos. 59-53836 and 59-71048, There are maleic acid copolymers, partially esterified maleic acid copolymers and the like, and similarly there are acidic cellulose derivatives having a carboxylic acid in the side chain. In addition to this, a polymer having a hydroxyl group and an acid anhydride added thereto is also useful.

  Of these, multi-component copolymers with benzyl (meth) acrylate / (meth) acrylic acid / and other monomers are particularly preferred. In addition, 2-hydroxyethyl methacrylate, polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful as the water-soluble polymer. Moreover, in order to raise the intensity | strength of a cured film, alcohol soluble nylon, the polyether of 2, 2-bis- (4-hydroxyphenyl) propane, and epichlorohydrin can also be contained.

  Examples of the acrylic copolymer include a multi-component copolymer of benzyl (meth) acrylate / (meth) acrylic acid / and other monomers, and 2-hydroxypropyl (meth) described in JP-A-7-140654. Acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene Macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, and the like. The development characteristics of the composition of the present invention can be further improved by using two or more of these acrylic copolymers together.

-Photopolymerization initiator-
The photopolymerization initiator in the present invention is not particularly limited as long as it can polymerize the photopolymerizable compound. Conventionally known photopolymerization initiators can be used.

  Examples of the photopolymerization initiator include active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine, 3-aryl-substituted coumarin compounds, and at least one lophine dimer.

  Among the active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine, the halomethyloxadiazole compound is 2-halomethyl-5 represented by the following general formula IV described in JP-B-57-6096. -Vinyl-1,3,4-oxadiazole compounds are mentioned.

In general formula IV, W represents a substituted or unsubstituted aryl group, and X represents a hydrogen atom, an alkyl group, or an aryl group. Y represents a fluorine atom, a chlorine atom or a bromine atom. n represents an integer of 1 to 3.
Specific compounds of the general formula IV include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4- Examples include oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole.

  Examples of the halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds represented by the following general formula V described in JP-B-59-1281, and the following general formulas described in JP-A-53-133428. 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by VI and 4- (p-aminophenyl) -2,6-di-halomethyl represented by the following general formula VII -S-triazine compound is mentioned.

In general formula V, Q represents Br or Cl. P is, -CQ ₃ (Q is as defined _{above), - NH 2, -NHR,} -N (R) 2, or -OR (wherein, R represents a phenyl or alkyl group). n represents an integer of 0 to 3. W represents an aromatic group which may be substituted, a heterocyclic group which may be substituted, or a monovalent group represented by the following general formula VA.

  In the general formula VA, Z is —O— or —S—, and R is as defined above.

In the general formula VI, X represents Br or Cl. m and n are integers of 0-3.
R ′ represents a group represented by the following general formula VIA.

In the general formula VIA, R ₁ represents a hydrogen atom or ORc (Rc is an alkyl, cycloalkyl, alkenyl, aryl group), and R ₂ represents a Cl, Br, alkyl, alkenyl, aryl, or alkoxy group.

In general formula VII, R ₁ and R ₂ are the same or different and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a group represented by general formula VIIA or VIIB below. R ₃ and R ₄ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. X and Y are the same or different and each represents Cl or Br. m and n are the same or different and represent 0, 1 or 2.

In the general formulas VIIA and VIIB, R ₅ , R ₆ and R _{7 each} represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group. Examples of substituents in substituted alkyl groups and substituted aryl groups include aryl groups such as phenyl groups, halogen atoms, alkoxy groups, carboalkoxy groups, carboaryloxy groups, acyl groups, nitro groups, dialkylamino groups, sulfonyl derivatives, etc. Is mentioned.

In the general formula VII, R ₁ and R ₂ may form a heterocycle consisting of a nonmetallic atom together with the nitrogen atom bonded thereto, and in this case, examples of the heterocycle include those shown below. It is done.

  Specific examples of general formula V include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethyl). And aminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like.

  Specific examples of general formula VI include 2- (naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4, 6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) ) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [ 4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4, 6-bis-trichloromethyl-s-to Azine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy- Naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, etc. Can be mentioned.

  Specific examples of the general formula VII include 4- [p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-p -N, N-di (ethoxycarbonylmethyl) 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- (p- N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl)- -Triazine, 4- [p-N, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-chloroethylcarbonylaminophenyl) -2, 6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2 , 6-Di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloro) Methyl) -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-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6 -Di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro- p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -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 (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6- [3-bromo-4- [N, N-bis (ethoxycarbonylmethyl) amino] phenyl] -1,3,5-tri Examples include azine.

  The following sensitizers can be used in combination with these initiators. Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 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-methoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyrylketone, p- (dimethylamino) phenyl-p-methylstyrylketone, benzophenone, p- (dimethylamino) ) Benzophenone (or Mihira) Ketone), p- (diethylamino) benzophenone, benzoanthrone, 7- {L-4-chloro-6- (diethylamino) -S-triazinyl (2), 1-amino} -3-phenylcoumarin, etc. Examples thereof include benzothiazole compounds described in Japanese Patent No. 48516.

  Moreover, the said 3-aryl substituted coumarin compound is a compound shown, for example by the following general formula VIII.

R ₈ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms (preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group), and R ₉ represents a hydrogen atom or a carbon atom. An alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a group represented by the following general formula VIIIA (preferably a methyl group, an ethyl group, a propyl group, a butyl group, a group represented by the general formula VIIIA, particularly preferably Represents a group represented by the general formula VIIIA).
R ₁₀ and R ₁₁ are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group), or a haloalkyl group having 1 to 8 carbon atoms (for example, a chloromethyl group, Fluoromethyl group, trifluoromethyl group, etc.), C1-C8 alkoxy group (for example, methoxy group, ethoxy group, butoxy group), C6-C10 aryl group (for example, phenyl group) which may be substituted, amino A group, —N (R ₁₆ ) (R ₁₇ ), a halogen atom (for example, Cl, Br, F); Preferred are a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl group, -N (R ₁₆ ) (R ₁₇ ), and Cl.
R ₁₂ represents an optionally substituted aryl group having 6 to 16 carbon atoms (for example, phenyl group, naphthyl group, tolyl group, cumyl group). Examples of the substituent include an amino group, —N (R ₁₆ ) (R ₁₇ ), an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), and 1 to 8 carbon atoms. Haloalkyl group (for example, chloromethyl group, fluoromethyl group, trifluoromethyl group, etc.), C1-C8 alkoxy group (for example, methoxy group, ethoxy group, butoxy group), hydroxy group, cyano group, halogen atom (for example, Cl, Br, F).
R ₁₃ , R ₁₄ , R ₁₆ and R ₁₇ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group or an octyl group). R ₁₃ and R ₁₄ and R ₁₆ and R ₁₇ are bonded to each other to form a heterocyclic ring (for example, a piperidine ring, piperazine ring, morpholine ring, pyrazole ring, diazole ring, triazole ring, benzotriazole ring, etc.) together with a nitrogen atom. Also good.
R ₁₅ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy group, ethoxy group, butoxy group). Group), an optionally substituted aryl group having 6 to 10 carbon atoms (eg, phenyl group), amino group, N (R ₁₆ ) (R ₁₇ ), and halogen atom (eg, Cl, Br, F). Zb represents = O, = S or = C (R ₁₈ ) (R ₁₉ ). Preferably, = O, = S, = C (CN) ₂ , and particularly preferably = O. R ₁₈ and R ₁₉ are the same or different and each represents a cyano group, —COOR ₂₀ , or —COR ₂₁ . R ₂₀ and R ₂₁ are each an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), haloalkyl group having 1 to 8 carbon atoms (for example, chloromethyl group, fluoromethyl group, A trifluoromethyl group and the like, and an optionally substituted aryl group having 6 to 10 carbon atoms (for example, a phenyl group).

  Particularly preferred 3-aryl-substituted coumarin compounds are {(s-triazin-2-yl) amino} -3-arylcoumarin compounds represented by the general formula IX.

  Lophine dimer means 2,4,5-triphenylimidazolyl dimer composed of two lophine residues, and its basic structure is shown below.

  Specific examples thereof include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxy). Phenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, and the like.

Although it does not specifically limit as a photoinitiator of an oxime type compound, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (4-methylsulfanyl) -Phenyl) -butane-1,2-butane 2-oxime-O-acetate, 1- (4-methylsulfanyl-phenyl) -butan-1-one oxime-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) ) -Acetic acid ethyl ester-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O-benzoate, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) -1,2-octanedione and the like.
In the present invention, other known compounds can be used in addition to the above initiators.
For example, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, aromatics substituted with α-hydrocarbons disclosed in US Pat. No. 2,722,512 Group acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, triallyl disclosed in US Pat. No. 3,549,367 Combination of imidazole dimer / p-aminophenyl ketone, benzothiazole compound / trihalome disclosed in Japanese Patent Publication No. 51-48516 Thial-s-triazine compounds are exemplified.
Further, Adeka optomer SP-150, 151, 170, 171, N-1717, N1414, etc. manufactured by Asahi Denka Co., Ltd. can be used as the polymerization initiator.

  In this invention, the usage-amount of a photoinitiator is 0.1-10.0 mass% of the total solid of the composition of this invention, Preferably it is 0.5-5.0 mass%. When the amount of the initiator used is less than 0.1% by mass, the polymerization is difficult to proceed, and when it exceeds 10.0% by mass, the film strength is weakened.

-Solvent-
The solvent used as necessary in the composition of the present invention is appropriately selected according to the solubility, applicability, and safety of the composition.
Solvents used in preparing the composition of the present invention include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate. Butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-oxypropion 3-oxypropionic acid alkyl esters such as methyl acid and ethyl 3-oxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2- Oxypro Methyl onate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropion Ethyl acetate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate , Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones For example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene and xyres.

  Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol monomethyl ether acetate and the like are preferably used.

  These solvents may be used alone or in combination of two or more.

-Other ingredients-
The composition of the present invention has various conventionally known additives such as fillers, polymer compounds other than the above alkali-soluble resins, surfactants, and pigments for the purpose of improving the dispersibility of the colorant or as required. A dispersant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like can be blended.

  Specific examples of these additives include fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, hydroxyl group A polymer having an acid anhydride added thereto, an alcohol-soluble nylon, an alkali-soluble resin such as a phenoxy resin formed from bisphenol A and epichlorohydrin; a nonionic, a kachin-based, an anionic surfactant, etc. Specifically, a phthalocyanine derivative (commercially available product EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and W001 (manufactured by Yusho); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxy Ethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (BASF Corporation Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 Nonionic surfactants such as W004, W005, W017 (manufactured by Yusho) and the like; EFKA-46, EFKA-47, EFKA-47EA, EF Polymer dispersion such as A polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (Sannopco) Agents: Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, and other various Solsperse dispersants (manufactured by Zeneca); L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka) and Isonet S-20 (Sanyo Kasei);

Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Adhesion promoters such as methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;
Antioxidants such as 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone;
And an aggregation inhibitor such as sodium polyacrylate.

  In addition, when promoting the alkali solubility in the unirradiated part and further improving the developability of the composition of the present invention, the composition of the present invention is an organic carboxylic acid, preferably a low molecular weight having a molecular weight of 1000 or less. An organic carboxylic acid can be added. Specifically, aliphatic 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 Aliphatic dicarboxylic acids such as acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as carbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

In addition to the above, it is preferable to add a thermal polymerization inhibitor to the composition of the present invention. For example, hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol , T-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. Is useful.

-Manufacturing method of photocurable composition-
The photocurable composition of the present invention comprises the colorant, the alkali-soluble resin, the photopolymerizable compound, the photopolymerization initiator, and the other components used as necessary by mixing with the solvent. It can be prepared by mixing and dispersing using a disperser.
The mixing and dispersing step preferably includes kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

In the kneading and dispersing step, the surface of the colorant particles of the raw material is promoted to wet with the constituent components mainly composed of the resin component of the vehicle, and the solid colorant particles and vehicle solution are solidified from the solid / gas interface between the colorant particles and air. / Convert to solution interface.
In the fine dispersion step, the colorant particles are dispersed to a fine state close to the primary particles by mixing and stirring together with a dispersion medium for fine particles of glass or ceramic.
Therefore, in the kneading and dispersing step, it is necessary to convert the interface formed by the colorant particle surface from air to a solution. Therefore, a strong shearing force and compressive force are required. desirable.
On the other hand, in the fine dispersion step, it is necessary to uniformly and evenly distribute the particles to a fine state, and a disperser that gives impact force and shear force to the agglomerated colorant particles, A relatively low viscosity is desirable.
The uniform and stable dispersion means that the antireflection film pattern for solid-state imaging device formed on the substrate is uniformly dispersed so as not to cause unevenness in the antireflection effect so as not to generate protrusions. The average primary particle diameter (particle size) of the black colorant in the photocurable composition is preferably in the above range.
The average primary particle size can be measured using electron microscopy.

In the kneading and dispersing step in the production of the photocurable composition of the present invention, for example, first, a black colorant, a dispersant or a surface treatment agent, an alkali-soluble resin, and a solvent are kneaded. The machines used for kneading are two rolls, three rolls, ball mills, tron mills, dispersers, kneaders, kneaders, homogenizers, blenders, single-screw and twin-screw extruders, etc., which disperse while giving a strong shearing force.
Next, a solvent and an alkali-soluble resin (the remainder used in the kneading step) are added, and a particle size of 0.1 to 1 mm is mainly used using a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc. It is finely dispersed with beads made of glass, zirconia or the like.
It is possible to omit this kneading step. In that case, beads are dispersed with a pigment and a dispersant or a surface treatment agent, an alkali-soluble resin and a solvent. In this case, the remaining alkali-soluble resin in the kneading step is preferably added during the dispersion.
For details on kneading and dispersing, see T.W. C. Also described in “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964).

≪Antireflection film≫
The antireflection film of the present invention has a width of 1.5 μm or less created on the substrate using the photocurable composition, or is created on the substrate using the photocurable composition. It is an antireflection film having a thickness of 1.0 μm or less.
Since the antireflection film of the present invention has the above-described configuration, it has excellent adhesion to the ground, can reduce the generation of false signals due to stray light, and can have few color defects.
More specifically, it is formed on the substrate, directly on the light shielding film provided on the electrode and / or the charge transfer circuit of the solid-state imaging device having the electrode and the charge transfer circuit, or via another layer. For example, an antireflection film between RGB pixels of the color filter is preferable. These are not particularly limited.

The antireflection film of the present invention is formed using the photocurable composition.
Specifically, after the antireflective film formed by applying the photocurable composition on a substrate is dried (prebaked), it can be obtained through pattern exposure and alkali development processes.
More specifically, for example, the composition for forming an antireflection film is directly or via another layer on a substrate, on the electrode and / or the charge transfer circuit of a solid-state imaging device having an electrode and a charge transfer circuit. After drying (pre-baking) the photocurable coating film formed by coating by a coating method such as spin coating, slit coating, casting coating, roll coating or the like directly on the light shielding film provided on The coating film is exposed to light, and only the portion of the coating film irradiated with light is cured and developed with a developing solution, whereby a film is formed in a pattern on the light shielding film, whereby an antireflection film can be produced.
Although it does not specifically limit as a radiation used for this light irradiation, Although it can use, it can select a wavelength suitably based on the photoinitiator to be used. The light shielding film is not particularly limited, but is preferably an aluminum light shielding film.
Further, the insulating film is not particularly limited, and for example, a SiN thin film can be used.
As the radiation, it is possible to use radiation having an emission line spectrum for g-line (436 nm), h-line (405 nm), i-line (365 nm), j-line (310 nm), and the like.
The formation position of the antireflection film of the present invention in the solid-state imaging device includes (1) on a planarizing film on a silicon substrate, (2) between RGB pixels of a color filter, (3) on a light shielding film, and (4) a light shielding film. There are positions where the flattening film is blocked between the color filter pixels and (5) a position where the light shielding film is covered. However, other positions may be formed as long as the effects of the present invention are not impaired. Among these, it is preferable to form between the RGB pixels of the color filter via the planarizing film on the silicon substrate on the light shielding film.
The formation position will be described in the section of the solid-state imaging device described later.

The development is preferably an alkali development treatment, and the non-light-irradiated portion is eluted into the alkaline aqueous solution by the exposure, and only the photocured portion remains. As a developing solution, the photocurable film layer of the light non-irradiated part is dissolved. Any developer can be used as long as it does not dissolve the light irradiation part.
After the excess developer is removed by washing and drying, heat treatment (post-bake) can be performed at a temperature of 50 to 240 ° C. Thus, a photocuring film can be manufactured. Thereby, a light shielding film is obtained.
Since the photo-curable composition contains a black coloring material that exhibits a filler effect, the antireflection film of the present invention is excellent in workability without being deformed by heat treatment after film formation, and carbon black is used. When it becomes particularly prominent.

  Examples of the substrate include a photoelectric conversion element substrate used for a solid-state imaging element, for example, a silicon substrate, an organic semiconductor substrate, and the like. On these substrates, a photoelectric conversion element, a transfer register, a signal detection unit, a drive circuit are provided. A color filter that forms each pixel may be formed, such as a peripheral circuit.

  Drying (pre-baking) of the composition layer of the present invention applied on the substrate can be performed at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds with a hot plate, oven, etc., and at a temperature of 70 to 130 ° C. 60 to 180 seconds, preferably 90 to 120 ° C. and more preferably 90 to 120 seconds.

  The coating thickness (antireflection film after drying) of the composition of the present invention is generally 2.0 μm or less, but the photoelectric conversion element formed on a substrate such as a silicon wafer accompanying the miniaturization of pixels. From the viewpoint of thinning the effective optical functional layer from the upper surface (substrate surface) to the lower surface of the on-chip microlens, 1.0 μm or less is necessary, but 0.6 μm or less is more preferable, and 0.5 μm or less is most preferable. .

  The reflectance of the antireflection film of the present invention is 35% or less, preferably 25% or less, most preferably when the irradiation light is irradiated at an irradiation angle of 5 ° with a thickness of 0.5 μm and a wavelength region of 350 to 800 nm. Is 20% or less.

Any developer can be used as long as it dissolves the antireflection film for a solid-state imaging device of the present invention and does not dissolve the radiation irradiated portion. Specifically, a combination of various organic solvents and an alkaline aqueous solution can be used, and among them, an alkaline developer is preferably used.
Examples of the organic solvent include the aforementioned solvents used in preparing the composition of the present invention. The development temperature is usually 20 ° C. to 50 ° C., and the development time is 20 to 90 seconds.

  Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium. Concentration of an alkaline compound such as hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution dissolved so as to be% is preferably used. In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans (rinse) with water after image development.

The post-baking is a post-development heating for complete curing, and can usually be performed at a temperature of about 200 ° C. to 220 ° C. (hard baking).
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.
In addition to the post-bake treatment, the coating film may be cured by irradiating ultraviolet rays with a high-pressure mercury lamp or the like while heating (post-cure treatment).

  The width (line width) of the antireflection film of the present invention needs to be 1.5 μm or less from the viewpoint of miniaturization of a solid-state imaging device or the like, but is preferably as small as possible.

  An overcoat layer (flattening layer) can be provided on the color filter layer in the solid-state imaging device described later of the present invention. Examples of the resin (OC agent) that forms the overcoat layer include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition. Above all, it excels in transparency in the visible light region, and when the resin component of the photocurable composition for color filters and the resin component of the photocurable composition are mainly composed of an acrylic resin, the adhesion is improved. From the standpoint of superiority, an acrylic resin composition is desirable. In particular, a photo-curable (meth) acrylic resin for a photoresist used in a color filter is preferable because matching with the manufacturing process of the color filter is improved.

≪Solid-state imaging device (image sensor) ≫
The solid-state imaging device of the present invention has the antireflection film of the present invention. The other configuration is not particularly limited, and a conventionally known configuration can be adopted.
Although the solid-state image sensor of this invention is demonstrated below using FIGS. 1-2, it is not limited to this.

  FIG. 1 is a configuration diagram showing an example of a solid-state imaging device of the present invention. FIG. 2 is a cross-sectional view of a preferred embodiment of the solid-state imaging device of the present invention when the antireflection film of the present invention is formed at a position immediately above the transfer electrode on the planarizing film on the silicon substrate. In addition, the same code | symbol is provided and demonstrated to what has the substantially same function.

As shown in FIG. 1, the solid-state imaging device of the present invention has a plurality of light receiving sensor portions (photoelectric conversion portions PD) 2 that perform photoelectric conversion on the surface layer portion of a substrate made of a silicon substrate 1 (see FIG. 1). 2).
In addition, a vertical transfer register 3 having a CCD structure for transferring charges formed by the light receiving sensor unit 2 is provided adjacent to the light receiving sensor unit 2, and a horizontal transfer is provided at one end of the vertical transfer register 3. A register 4 is provided.
A signal detection unit and an output amplifier are formed at the final stage of the horizontal transfer register 4, and a peripheral circuit unit A such as a drive circuit is formed in the peripheral unit. On the vertical transfer register 3 and the horizontal transfer register 4 of the CCD structure, a light shielding film for peripheral circuits (not shown, see 6 in FIG. 2) via an interlayer film (not shown, see the insulating film 13 in FIG. 2). .) Is formed by a sputtering apparatus.

FIG. 2 is a cross-sectional view of one embodiment of the solid-state imaging device of the present invention, and a photoelectric conversion element (light receiving sensor unit) 2 for storing light by converting it into electric charges is provided on the surface layer portion of the silicon substrate 1. In addition, a transfer electrode 5 having a CCD structure is provided to transfer charges adjacent to the light receiving sensor portion (photoelectric conversion element portion) 2. Further, a light shielding film 6 is provided on the upper layer so as to cover the transfer electrode 5. The transfer electrode 5 is covered with an insulating film 13 or the like.
Further, a flattening film 7 is provided on the entire silicon substrate on which the light shielding film 6 is formed, if necessary. An insulating film 13 is usually formed between the planarizing film 7 and the silicon substrate 1.
The antireflection film 8 is preferably provided directly above (directly above) the light shielding film 6 via the flattening film 7 or directly without using the flattening film 7.

Further, a color filter 9 having three colors of R, G, and B for forming color pixels is provided on the silicon substrate on which the antireflection film 8 and the flattening film 7 are formed. The RGB pixels are positioned so that the center of each pixel is directly above the center of the light receiving sensor unit 2, and a part of each of the two sides of each color filter pattern overlaps the antireflection film 8 on the antireflection film 8. This is preferable in terms of improving the aperture ratio.
The maximum side of the rectangular unit pixel for each color of the color filter 9 is generally 1.5 to 20 μm or less, and among them, the effective use of a substrate such as a silicon wafer, the miniaturization of a device using a solid-state imaging device, among others. Is preferably 5 μm or less, more preferably 4 μm or less, and particularly preferably 3 μm or less from the viewpoint of high speed operation of the solid-state imaging device.

  A planarizing film 10 is provided on the color filter 9. Furthermore, it is preferable that an on-chip microlens 11 for condensing is formed.

  The solid-state imaging device of the present invention is characterized by having the antireflection film, and the form thereof is not particularly limited, and many forms are possible.

  Next, although the manufacturing method of the solid-state image sensor of this invention is demonstrated using FIG. 2, it does not specifically limit, Any well-known manufacturing method can be used. Other forms other than the form shown in FIG. 2 can be manufactured by the same method.

(Circuit part formation)
A substrate having peripheral circuit parts such as a light receiving sensor part 2, a charge transfer part 12 (transfer electrode 5 and the like), a signal detection part, an output amplifier, and a drive circuit in the surface layer part of the silicon substrate 1 is formed. The substrate can be produced by a conventionally known method.

  A light shielding film 6 is formed on the entire surface of the substrate directly or via an interlayer film (insulating film) 13. Subsequently, after a positive resist is applied to the entire surface, exposure / development is performed through a mask to expose the light-shielding film 6 located on the upper side of the light-receiving sensor unit 2 to be removed in a later etching process. Further, after etching with a dry etcher, the remaining resist is peeled off to expose a portion of the light shielding film 6 that covers the transfer electrode.

(Formation of planarization film)
After the planarization film composition is uniformly applied on the substrate, the substrate is heated with a hot plate to form the planarization film 7.

(Creation of antireflection film)
The photocurable composition is uniformly applied on the silicon substrate on which the light shielding film 6 is formed.
For example, when spin coating is used, the coating rotational speed is adjusted so that the film thickness from the front surface of the light-shielding film 6 after the heat treatment on the hot plate at a surface temperature of 90 ° C. for 120 seconds is 0.5 μm after coating. The film thickness can be adjusted. In addition, before applying the photocurable composition, an oxide film such as an anodizing treatment or a boehmite treatment may be formed on the light shielding film 6 to improve adhesion.
Next, the substrate coated with the photocurable composition is heat-treated (for example, hot plate at 90 ° C. for 120 seconds) to form a dry coating film.
Next, radiation (for example, i-line stepper, FPA-3000i5 + manufactured by Canon Inc.) is exposed through a mask for forming a pattern of the antireflection film 8 on the light shielding film 6, and development (for example, 23 ° C., 60 Second, tetramethylammonium hydroxide (TMAH) 0.3% aqueous solution), then rinsed with pure water (for example, 20 seconds spin shower), washed with water, dried, and then image pattern of antireflection film 8 (For example, a line width of 0.5 μm) is obtained.

A blue color resist (COLOR MOSAIC-EXIS SB-4000L manufactured by FUJIFILM Electronics Materials Co., Ltd.) is uniformly applied to the substrate on which the antireflection film 8 is formed.
After the application, for example, heat treatment is performed with a hot plate at a surface temperature of 100 ° C. for 120 seconds.
Radiation exposure (for example, i-line stepper, FPA-3000i5 + manufactured by Canon Inc.) and tetramethylammonium hydroxide (TMAH) 0.3% through a mask having a pattern in which square pixels each having a side of 2 μm are arranged Paddle development is performed using an aqueous solution at 23 ° C. for 60 seconds, followed by rinsing with pure water for 20 seconds using a spin shower, followed by washing with pure water.
Thereafter, the attached water droplets are removed by blowing air, and the substrate is naturally dried to obtain a blue color filter pattern 9B. At this time, it is preferable that a part of two sides of the pixel pattern of the adjacent color filter overlaps the antireflection film 8 so as to overlap the antireflection film 8.
Repeat the same process for Green (using COLOR MOSAIC-EXIS SG-4000L manufactured by FUJIFILM Electronics Materials Co., Ltd.) and Red (using COLOR MOSAIC-EXIS SR-4000L manufactured by FUJIFILM Electronics Materials Co., Ltd.). The color filters 9G and 9R are obtained on the light receiving sensor portion 2 on the substrate.

  A flattening film composition (COLOR MOSAIC CT-3100L manufactured by FUJIFILM Electronics Materials Co., Ltd.) is uniformly applied on the silicon substrate on which the color filter 9 is formed, and the substrate is heated at 220 ° C. at 4 ° C. The planarization film 10 is formed by heating for a minute. Further, the microlens 11 is formed thereon. The obtained silicon substrate is subjected to dicing and packaging to obtain a solid-state imaging device.

  Hereinafter, the present invention will be specifically described with reference to examples, but the contents of the present invention are not limited thereto. In Examples, parts and% mean parts by mass and% by mass unless otherwise specified.

Example 1
<Solid-state imaging device (when using monomer having bisphenol as skeleton and (meth) acryloyl group)>
[Circuit part creation]
As shown in FIGS. 1 and 2, the solid-state imaging device has a plurality of light receiving sensor portions 2 that perform photoelectric conversion on a surface layer portion of a substrate made of a silicon substrate 1, and this light receiving sensor portion is adjacent to the light receiving sensor 2. 2 is provided with a vertical transfer register of CCD structure for transferring the electric charge formed at 2, a horizontal transfer register 4 for transferring in the horizontal direction is provided at one end of the column of the vertical transfer register 3, and a signal is detected at the final stage of the horizontal transfer register A part (not shown) and an output amplifier (not shown) are formed, and a peripheral circuit part A such as a drive circuit is formed in the peripheral part.
An aluminum light-shielding film 6 was formed on the entire surface of the substrate on which the peripheral circuits and the like were formed via an interlayer film (insulating layer 13) with a sputtering apparatus.
Further, after applying a positive resist on the entire surface, exposure and development were performed through a mask to expose the aluminum light-shielding film 6 to be removed in a later etching process. Further, after etching with a dry etcher, the remaining resist was peeled off to expose the aluminum light-shielding film 6.

[Formation of planarization film]
A flattening film agent (COLOR MOSAIC CT-3100L manufactured by FUJIFILM Electronics Materials Co., Ltd.) is uniformly applied on the silicon substrate on which the circuit portion has been formed, and then the substrate is heated at 220 ° C. at 220 ° C. A flattening film 7 having a thickness of 1 μm was formed by ripening for a minute.

[Preparation of photosensitive composition for forming antireflection film]
(Preparation of carbon black dispersion)
The carbon black dispersion used in the photosensitive composition for forming an antireflection film was obtained by subjecting the following composition 1 of carbon black dispersion to high viscosity dispersion treatment with two rolls to obtain a dispersion. The viscosity of the dispersion at this time was 70000 mPa · s.
The following carbon black dispersion composition 2 was added to the dispersion, and the mixture was stirred for 3 hours using a homogenizer at 3000 rpm. The obtained mixed solution was subjected to a fine dispersion treatment for 4 hours with a disperser (trade name: Dispermat GETZMANN) using 0.3 mm zirconia beads to prepare a carbon black dispersion. At this time, the viscosity of the mixed solution was 37 mPa · s.

(Composition 1 of carbon black dispersion)
Average primary particle size 15nm carbon black (PigmentBlack 7)
Propylene glycol monomethyl ether acetate solution of 23 parts benzyl methacrylate / methacrylic acid copolymer (BzMA / MAA = 70/30 molar ratio, weight average molecular weight Mw: 30000, solid content: 45%) 22 parts Solsperse 5000 (manufactured by GENECA) Dispersant) 1.2 parts

(Composition 2 of carbon black dispersion)
Propylene glycol monomethyl ether acetate solution of pendyl methacrylate / methacrylic acid copolymer (BzMA / MAA = 70/30 molar ratio, weight average molecular weight Mw: 30000, solid content: 45%) 22 parts Propylene glycol monomethyl ether acetate 200 parts

(Preparation of photosensitive composition for forming antireflection film)
The following components were mixed with a stirrer to prepare a photosensitive composition for forming an antireflection film.
(Composition of photosensitive composition for forming antireflection film)
Cyclomer P (alkali-soluble resin: acrylic copolymer propylene glycol monomethyl ether acetate 50% solution, manufactured by Daicel Chemical Industries, Ltd., weight average molecular weight: 20,000, acid value: 30) 1.8 parts dipentaerythritol hexa Acrylate 1.5 parts NK-ester ABPE-10 (bisphenol A compound, manufactured by Shin-Nakamura Chemical Co., Ltd., photopolymerizable compound) 1.5 parts Carbon black dispersion 12.5 parts above 12.5 parts propylene glycol monomethyl Ether acetate 18 parts Ethyl-3-ethoxypropionate 11.5 parts 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) 0.6 parts

[Creation of antireflection film]
The antireflection film-forming photosensitive composition was adjusted so that the coating rotation speed of spin coating was 0.5 μm after the heat treatment on the hot plate at a surface temperature of 90 ° C. for 120 seconds after coating, It apply | coated uniformly on the board | substrate with which the planarizing film was formed.
Next, the substrate coated with the anti-reflective coating forming photosensitive composition was heat-treated with a hot plate at 120 ° C. for 120 seconds to form a dry coating film.
Next, exposure is performed with an i-line stepper, FPA-3000i + manufactured by Canon Inc., through a mask for forming a grid pattern having a line width of 0.5 μm on the aluminum light-shielding film 6, and tetramethylammonium hydroxide (TMAH ) Paddle development was performed for 60 seconds at 23 ° C. using a 0.3% aqueous solution, and then rinsed with pure water for 20 seconds in a spin shower, followed by washing with pure water. Thereafter, the adhering water droplets were removed by blowing high-level air, the substrate was naturally dried, and an image pattern of the antireflection film 8 was obtained.
The pattern shape obtained at this time is shown in FIG.

[Create color filter]
Using a blue color resist (COLOR MOSAIC-EXIS SB-4000L manufactured by FUJIFILM ELECTRONICS MATERIALS) on the substrate on which the antireflection film 8 is formed, the coating rotation speed during spin coating is The film thickness from the planarization film 8 after the heat treatment on the hot plate at a temperature of 100 ° C. for 120 seconds was adjusted to 1.1 μm, and the film was uniformly applied on the substrate on which the antireflection film 8 was formed.
It is exposed with an i-line stepper, FPA-3000i + manufactured by Canon Inc., through a mask pattern in which square pixels with sides of 2 μm are arranged, and developed with a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH). , Blue color filter pattern 9B was obtained. At this time, the pattern was formed so as to be embedded in the frame of the antireflection film 8.
Repeat the same process for Green (using COLOR MOSAIC-EXIS SG-4000L manufactured by FUJIFILM Electronics Materials Co., Ltd.) and Red (using COLOR MOSAIC-EXIS SR-4000L manufactured by FUJIFILM Electronics Materials Co., Ltd.). Color filters 9R and 9G were obtained on the light receiving sensor portion 2 on the substrate.

[Formation of flattened film on color filter, creation of solid-state image sensor]
A leveling film agent (COLOR MOSAIC CT-3100L manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied onto the silicon substrate on which the color filter 9 is formed, and then the substrate is heated at 220 ° C. on a hot plate. For 4 minutes to form a planarizing film 10. Further, a microlens 11 was formed thereon.
The obtained silicon substrate was subjected to dicing packaging to obtain a solid-state imaging device.

(Example 2)
<Solid-state imaging device (when a monomer having an isocyanuric ring as a skeleton and a (meth) acryloyl group)>
In “Preparation of Photosensitive Composition for Forming Antireflection Film” in Example 1, “NK-ester ABPE-10 (manufactured by Shin-Nakamura Chemical Co., Ltd.)” was designated as “M315 (isocyanuric acid triacrylate, A solid-state imaging device was produced in the same manner as in Example 1 except that the product was changed to “Toagosei Co., Ltd.”. Here, the image pattern shape of the antireflection film formed using the photosensitive composition for forming an antireflection film obtained in the intermediate step is shown in FIG.

(Example 3)
In “Preparation of photosensitive composition for formation of antireflection film” in Example 1, “NK-ester ABPE-10” which is a photopolymerizable compound was changed to “tri- (acryloyloxyethoxyethyl) -isocyanurate”. A solid-state imaging device was manufactured in the same manner as in Example 1 except that. Here, the image pattern shape of the antireflection film formed using the photosensitive composition for forming an antireflection film obtained in the intermediate step is shown in FIG.

(Comparative Example 1)
<Solid-state imaging device (when the monomer mentioned in the present invention is not used)>
In “Preparation of photosensitive composition for formation of antireflection film” in Example 1, the photopolymerizable compound was changed from “NK-ester ABPE-10 1.5 parts” to “3.0 parts of dipentaerythritol hexaacrylate”. A solid-state imaging device was produced in the same manner as in Example 1 except that. Here, the image pattern shape of the antireflection film formed using the photosensitive composition for forming an antireflection film obtained in the intermediate step is shown in FIG.

3 to 6 are image patterns in which the lattice-like portions are antireflection films. In FIG. 6, which is a comparative example, the lattice is distorted. This indicates that since the adhesion between the antireflection film and the substrate is poor, the antireflection film floats away from the substrate during development. On the other hand, no distortion of the lattice was observed in FIGS.
For this reason, the grid pattern with improved distortion could be covered with the black antireflection film without protruding on the transfer electrode. In addition, since the color filter elements are separated from each other, the light beam that has passed through the color filter of the adjacent pixel is prevented from entering the photodiode that should not enter (e.g., the light that has passed through the green color filter is In other words, it is possible to reduce the output of color signals that cannot be seen in the original captured image. The effect was particularly noticeable around the image.
On the other hand, in the comparative example, it protruded from the transfer electrode or the transfer electrode was exposed, and it was difficult to manufacture a color solid-state imaging device.
Further, using the antireflection film of the comparative example, a device was assembled as a monochrome solid-state imaging device without producing a color filter. When imaging was performed using this, there was variation in the signal output from the pixels, and unevenness between the pixels was seen in the captured image.

It is a block diagram which shows an example of the solid-state image sensor of this invention. It is sectional drawing which shows an example of the solid-state image sensor at the time of forming the antireflection film of this invention between the RGB pixels of a color filter. It is the schematic at the time of observing the image pattern of the antireflection film obtained in Example 1 with SEM (scanning electron microscope). It is the schematic at the time of observing the image pattern of the antireflection film obtained in Example 2 with SEM (scanning electron microscope). It is the schematic at the time of observing the image pattern of the antireflection film obtained in Example 3 with SEM (scanning electron microscope). It is the schematic at the time of observing the image pattern of the anti-reflective film obtained by the comparative example 1 with SEM (scanning electron microscope).

Explanation of symbols

1 Silicon substrate 2 Light receiving sensor (PD)
3 Vertical transfer register (CCD)
4 Horizontal transfer register (CCD)
5 Transfer electrode 6 Shading film 7 Flattening film (on silicon substrate)
8 Antireflection film 9 Color filter (R, G, B)
DESCRIPTION OF SYMBOLS 10 Color filter top planarizing film 11 Micro lens 12 Charge transfer part 13 Insulating film A Peripheral circuit parts, such as a drive circuit

Claims (7)

A photocurable composition containing a colorant, a photopolymerizable compound, a photopolymerization initiator, and an alkali-soluble resin, wherein the photopolymerizable compound contains at least one of a bisphenol compound and an isocyanuric ring-containing compound. Sex composition. The photocurable composition of Claim 1 containing the carbon black whose average primary particle diameter of the said coloring agent is 10 nm or more and 30 nm or less. The photocurable composition according to claim 1 or 2, wherein the colorant contains a plurality of colors of organic pigments. The photocurable composition according to any one of claims 1 to 3, wherein the photopolymerizable compound contains at least one of the following general formulas (I) and (II).

(In the general formula (I), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ³ and R ⁴ each independently represents an ethylene group or a propylene group, m and n each independently represent an integer of 1 or more and m + n represents an integer of 3 to 40, and A ¹ and A ² each independently represents an acryloyl group or an allyl group.

(In the general formula (II), R ¹ , R ² and R ³ each independently represents an ethylene group or a propylene group, and a, b and c each independently represents an integer of 0 to 6. m, n, l Are each an integer, and m + n + 1 represents an integer of 0 to 18, and A ¹ , A ² and A ³ each independently represents an acryloyl group or an allyl group.) An antireflection film having a width of 1.5 µm or less, which is formed on a substrate using the photocurable composition according to any one of claims 1 to 4. An antireflection film having a thickness of 1.0 μm or less, which is formed on a substrate using the photocurable composition according to claim 1. A solid-state imaging device having the antireflection film according to claim 5.

Images