KR20040047714A - Thermosetting Composition, Halation Preventing Film of Solid State Imaging Device and Process for Forming the Same, and Solid State Imaging Device - Google Patents

Abstract

PURPOSE: Provided are a thermosetting composition to efficiently inhibit diffused reflection of a substrate and to obtain a high transmission rate of visual light and heat-resistance of a halation preventing film of a solid imaging device and a process for forming the film, and solid state imaging device. CONSTITUTION: The thermosetting composition comprises: (A) a copolymer of epoxy group containing a unsaturated compound and a monomer mixture containing a radical polymerization compound having radiation absorbing group; and (B) at least one compound selected from a group consisting of polyvalent carboxylic acid and anhydride thereof. The thermosetting composition is used for production of halation prevention film that comprises steps of forming a thermosetting composition film on a substrate; and heating the film.

Description

Thermosetting Composition, Halation Preventing Film of Solid State Imaging Device and Process for Forming the Same, and Solid State Imaging Device

The present invention relates to a thermosetting composition, an anti-halation film for a solid-state image sensor, a method for forming the same, and a solid-state image sensor.

The solid-state imaging device includes a MOS (Metal 0xide Semiconductor) type, a CCD (Charge Coupled Device) type, and the like, and each has a one-dimensional solid-state imaging device and a two-dimensional solid-state imaging device. As an example of the former, a facsimile etc. are mentioned, for example, a video camera etc. are mentioned as an example of the latter.

In recent years, such solid-state imaging devices have undergone digitalization and are required to have high image quality in accordance with the user's high quality orientation. An example is an increase in the number of pixels of a digital camera.

Although the solid-state image sensor has black-and-white color and color use, the solid-state image sensor for color is manufactured by forming a color filter of three colors on the board | substrate with which the solid-state image sensor was formed. Although the solid-state image sensor is used as it is, the convex-type lens (microlens) is provided in the surface corresponding to each solid-state scratching element, and the sensitivity (condensing ability) is improved (refer Unexamined-Japanese-Patent No. 3-223702). ).

In order to equip a solid-state image sensor with a color filter and / or a microlens, it is performed by forming a fine pattern using the lithographic technique using the photosensitive material.

The formation of the microlens is formed on a substrate on which a solid-state image sensor is formed and, if necessary, on a substrate on which a color filter is formed. Then, the transparent resin blocks left after developing and washing are heated, slightly melted and shrunk to form each block in the shape of a convex lens.

In the process of forming the color filter or the microlens, when the photosensitive material is exposed and patterned, the diffused light from the base substrate is exposed to a portion not to be exposed, and the actual pattern size is different from the desired size. There was a problem that a phenomenon, that is, "halation" occurred.

In the case of a microlens, when this phenomenon occurs, the shape of the lens becomes uneven and flickering occurs, which adversely affects image quality. This has become a more serious problem as the cell size of a solid-state image sensor becomes smaller than in recent years.

With respect to this problem, a method of suppressing reflection and preventing halation by forming an antireflection film on a solid-state imaging element substrate that absorbs radiation for lithography is known. In this example, a dye is incorporated into a CCD protective film using polyglycidyl methacrylate as a main component and trimellitic acid as a curing agent (see Japanese Patent No. 2956210). However, in the antireflection film, a part of the dye sublimes in the antireflection film to significantly reduce the anti-halation effect during the firing step performed to crosslink and solidify the applied material, or as the nonvolatile dye, the dye rises onto the protective film. There existed a fault that the microlens formed on the anti-halation film may not be formed in a desired shape.

Furthermore, the anti-halation film containing the copolymer of a unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, an epoxy group containing radically polymerizable compound, a mono and / or diolefin type unsaturated compound, and a radiation absorbing compound A proposal is made (see Japanese Patent Laid-Open No. 06-289201). This anti-halation film assumes the process whose temperature history after formation is 150 degrees C or less, and has not been verified about the heat resistance in the temperature exceeding 150 degreeC.

However, in the color solid-state image sensor, since the color filter material which used the conventional dye substrate is used, the color filter was able to harden | cure at the comparatively low temperature about 150 degreeC. However, in recent years, in response to the request for high precision, since a pigment-based material has been generally used, a curing temperature of 180 ° C. or higher is required in the formation step (Japanese Patent Laid-Open No. 11-211911, Japanese Patent Laid-Open) See Japanese Patent Application Laid-Open No. 11-258415 and Japanese Patent Laid-Open No. 2000-111722. Therefore, in the color solid-state image sensor, the anti-halation film formed before a color filter increases compared with the past, and exposes to high temperature. As a conventionally known anti-halation film material, it is known that when it is exposed to such a high temperature, it will not function as an anti-halation film. This phenomenon is presumably lowered in the radiation absorbing ability because the radiation absorbent blended in the antihalation film material sublimes and diffuses in the high temperature region exceeding 150 ° C.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to effectively suppress diffuse reflection light from a base substrate in an exposure step when forming a color filter or a microlens in a solid-state imaging device, The present invention provides a thermosetting composition suitable for forming an anti-halation film having a heat resistance, a method of forming an anti-halation film using the same, and a solid-state imaging device having the anti-halation film formed by the method and the anti-halation film.

1 is a schematic diagram showing the shape of a microlens pattern.

According to the present invention, the above object of the present invention is, firstly, [A] (a1) an epoxy group-containing unsaturated compound (hereinafter also referred to as "compound (a1)") and (a2) a radically polymerizable compound having a radiation absorbing group ( Hereinafter, a copolymer of a monomer mixture containing "compound (a2)" (hereinafter also referred to as "copolymer [A]"), and [B] polyhydric carboxylic anhydride and polyhydric carboxylic acid It is achieved by the thermosetting composition characterized by containing 1 or more types of compounds (henceforth "the" B component ") chosen from the group which consists of these.

Moreover, the said objective of this invention is 2nd achieved by the formation method of the anti-halation film | membrane of the solid-state image sensor characterized by including the following process [1] and [2] at least.

[1] forming a coating film of the above-mentioned thermosetting composition on a substrate, and

[2] A step of heat treating the coating film.

Further, the above object of the present invention is thirdly achieved by the anti-halation film of the solid-state image sensor formed by the above method, and fourthly by the solid-state image sensor having the anti-halation film.

According to the present invention, in the exposure step when forming a color filter or a microlens in a solid-state image sensor, halides can effectively suppress diffuse reflection light from the base substrate, have high transmittance of visible light, and have high heat resistance. Provided are a thermosetting composition suitable for forming a protective film, a method of forming an anti-halation film using the same, and a solid-state imaging device having the anti-halation film formed by the method and the anti-halation film thereof.

The anti-halation film of the present invention can effectively suppress diffuse reflection light from the base substrate in the exposure step when forming a color filter or microlens on the anti-halation film, and has high heat resistance. Therefore, the color filter and microlens formed on the anti-halation film of the solid-state image sensor of this invention can be made into the desired shape and size.

In addition, the solid-state imaging device of the present invention has the above-described anti-halation film. Since the color filter and the microlens formed on the anti-halation film are of the desired shape and size, the solid-state imaging device of the present invention is excellent in reliability.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated. First, each component of the thermosetting composition of this invention is explained in full detail.

Copolymer [A]

The copolymer [A] used in the present invention preferably contains 50 to 95% by weight, particularly preferably 60 to 90% by weight of the structural unit derived from the compound (a1). The copolymer whose structural unit is less than 50 weight% tends to reduce the moisture heat resistance of the anti-halation film obtained. On the other hand, when it exceeds 95 weight%, there exists a tendency for the storage stability of curable composition to fall.

The compound (a1) is a compound having an epoxy group and a polymerizable carbon-carbon double bond in one molecule, and specifically, for example, glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α Glycidyl n-propyl acrylate, Glycidyl α-butyl acrylate, Acrylic acid-3,4-epoxybutyl, Methacrylic acid-3,4-epoxybutyl, Acrylic acid 6,7-epoxyheptyl, Methacrylic Acids-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like. Can be.

Of these, methacrylic acid glycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like are copolymerized. It is preferably used from the viewpoint of increasing the reactivity and the heat resistance and hardness of the resulting anti-halation film. These (a1) epoxy group containing unsaturated compounds are used individually or in combination.

The copolymer [A] used in the present invention preferably contains 1 to 40% by weight, particularly preferably 3 to 30% by weight of the structural unit derived from the compound (a2). When this structural unit is less than 1 weight%, antihalation performance may become inadequate. On the other hand, when this structural unit exceeds 40 weight%, there exists a tendency for the film formability of a coating film to fall.

As the radiation absorbing group of the compound (a2), one that absorbs light having a wavelength of 400 nm or less, particularly 365 nm, and which does not substantially absorb light in the visible region is preferably used. Examples of such radiation absorbing groups include groups having a benzotriazole structure, a salicylate structure, a benzophenone structure, a substituted acrylonitrile structure, a xanthine structure, a coumarin structure, a prabon structure, and a carcon structure, Of these, groups having a benzotriazole structure are more preferred.

Among the radiation absorbing groups having a benzotriazole structure, a structure represented by the following general formula (1) is particularly preferable.

As a radically polymerizable compound which has such a radiation absorbing group, the compound represented by following formula (2)-4 is mentioned, for example.

In the formula, R ¹ and R ² are the same or different, and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, a hydroxy group, a halogen atom, a carboxyl group or an alkoxycarbonyl group, and R ³ is An alkylene group having 2 to 10 carbon atoms is represented, and R ⁴ represents a hydrogen atom or a methyl group.

In the formula, the definition of R ⁴ is the same as above, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

In the formula, the definitions of R ³ , R ⁴ and R ⁵ are the same as described above, and R ⁶ represents an alkylene group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group.

In the formula (2), examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹ and R ² include, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group and tert. Carbon number such as -butyl group, n-pentyl group, tert-pentyl group (amyl group), n-hexyl group, tert-hexyl group, n-heptyl group, tert-heptyl group, n-octyl group, di tert-octyl group 1-8 linear or branched alkyl groups are mentioned. Among them, tert-alkyl groups having 4 to 8 carbon atoms such as methyl group, tert-butyl group, tert-pentyl group, tert-heptyl group, and ditert-octyl group are preferable.

Examples of the alkoxyl group having 1 to 8 carbon atoms represented by R ¹ and R ² include a methoxy group, an ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group and tert- C1-C8 linear or branched alkoxyl groups, such as a butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, and n-octyloxy group, are mentioned.

As a halogen atom represented by R <^1> and R <^2> , a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. are mentioned, for example. Of these, chlorine atoms are preferred.

Examples of the alkylene group having 2 to 10 carbon atoms represented by R ³ include an ethylene group, trimethylene group, propylene group, tetramethylene group, 1,1-dimethyltetramethylene group, butylene group, octamethylene group, octylene group, C1-C10 linear or branched alkylene groups, such as a decamethylene group and a decylene group, are mentioned. Among these, an ethylene group, a propylene group, etc. are preferable.

In the above formulas (3) and (4), examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁵ include the same as the alkyl group having 1 to 8 carbon atoms represented by R ¹ and R ² in the above formula (2), and are preferably the same. .

In the above formula (4), examples of the alkylene group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group represented by R ⁶ include, for example, a methylene group, an ethylene group, a trimethylene group, a 2-hydroxytrimethylene group, and 1-methyl. These groups substituted by C1-C4 linear or branched alkylene groups and hydroxyl groups, such as an ethylene group, a tetramethylene group, a 1-methyl trimethylene group, and a 1, 1- dimethylethylene group, are mentioned. Among them, those having 2 to 3 carbon atoms, such as ethylene group, trimethylene group and 2-hydroxy trimethylene group, are preferable.

In the present invention, among the radically polymerizable compounds having a radiation absorbing group represented by the above formulas (2) to 4, a radically polymerizable compound having a radiation absorbing group represented by the formula (2) is particularly preferably used.

In the radically polymerizable compound having a radiation absorbing group represented by the general formula (2), R ¹ is substituted at the 5 position of the benzotriazole ring as a hydrogen atom or a chlorine atom, and R ² is a hydrogen atom, a methyl group or a tert- having 4 to 8 carbon atoms. A radical having a radiation absorbing group which is an alkyl group (preferably a hydrogen atom, a methyl group or a tert-butyl group), R ³ is an alkylene group having 2 to 10 carbon atoms (preferably 2 to 3), and R ⁴ is a hydrogen atom or a methyl group Polymeric compounds are particularly preferred. As a specific example of the radically polymerizable compound which has such a radiation absorbing group, 2- (2'-hydroxy-5'-acryloxyethylphenyl) -2H-benzotriazole and 2- (2'-hydroxy-5) are mentioned, for example. '-Methacryloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-methacryloxypropylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5 '-Methacryloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methacryloxyethylphenyl) -5-chloro-2H -Benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-acryloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-methacryl Oxyhexylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methacryloxyethylphenyl) -2H-benzotriazole, etc. are mentioned.

Among these, 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole (hereinafter, also referred to as "monomer (a2-1)") represented by the following general formula (5), and Also referred to as 2- (2'-hydroxy-3'-tert-butyl-5'-methacryloxyethylphenyl) -2H-benzotriazole (hereinafter referred to as "monomer (a2-2)" represented by the following formula (6) Is preferably used. In this invention, a radiation absorbing olefin unsaturated compound can be used individually by 1 type or in mixture of 2 or more types.

The copolymer [A] used in the present invention is a copolymer of a monomer mixture having the compound (a1) and the compound (a2) as essential components as described above, but the monomer mixture is optionally (a3) (a1) and Olefinic unsaturated compounds (henceforth "a compound (a3)" hereafter) other than (a2) can be contained.

By using such a compound (a3) as a copolymerization component like a compound (a1) and a compound (a2), the advantage of the improvement of the storage stability of a thermosetting composition, and the heat resistance of the antihalation film obtained is acquired.

The copolymer [A] of the present invention may contain 50% by weight or less, preferably 40% by weight or less of the structural unit derived from the compound (a3).

When this structural unit exceeds 50 weight%, the anti-halation performance and chemical-resistance of the obtained anti-halation film may be insufficient.

The olefinically unsaturated compound of (a3) is a compound which does not have an epoxy group and a radiation absorbing group and has a polymerizable carbon-carbon double bond, and examples thereof include alkyl methacrylates, alkyl acrylates, and methacrylic cyclic alkyls. Esters, acrylic cyclic alkyl esters, methacrylic acid aryl esters, acrylic aryl esters, dicarboxylic acid diesters, indene derivatives, dicarbonyl imide derivatives, hydroxyalkyl esters, aromatic unsaturated compounds, conjugated products Dienes and other unsaturated compounds may be mentioned.

Specific examples thereof include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate and the like as methacrylic acid alkyl esters;

As alkyl acrylate ester, methyl acrylate, isopropyl acrylate, etc .;

As methacrylic acid cyclic alkyl esters, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, cyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (this technology Commonly used in the art as dicyclopentanyl methacrylate), dicyclopentanyloxyethyl methacrylate, isoboroyl methacrylate, and the like;

Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, cyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (acrylamide dicyclopentanyl as conventional name in the art) Called dicyclopentanyloxyethyl acrylate, isoboroyl acrylate, etc .;

As methacrylic acid aryl ester, Phenyl methacrylate, benzyl methacrylate, etc .;

As acrylic acid aryl ester, Phenyl acrylate, Benzyl acrylate, etc .;

Diethyl maleate, diethyl fumarate, diethyl itaconate, etc. as dicarboxylic acid diesters;

Indene derivatives, such as indene, 1-methylindene;

As dicarbonylimide derivatives, phenylmaleimide, benzylmaleimide, cyclohexyl maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimi Di--6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridyl) maleimide and the like;

2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc. as hydroxyalkyl esters;

As aromatic unsaturated compounds, styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy styrene, etc .;

1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like as conjugated dienes;

As other unsaturated compounds, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, etc. are mentioned, respectively.

Of these, methacrylic acid alkyl esters, methacrylic acid cyclic alkyl esters, acrylic acid cyclic alkyl esters, aromatic unsaturated compounds, conjugated dienes, and dicarbonyl imide derivatives are preferably used, and in particular, styrene and t-butyl meta From the viewpoint of the copolymerization reactivity and the heat resistance of the anti-halation film obtained, acrylate, dicyclopentanyl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, phenylmaleimide and cyclohexyl maleimide are obtained. desirable.

These compounds (a3) are used alone or in combination.

Preferable specific examples of the copolymer [A] used in the present invention include, for example, methacrylate glycidyl / monomer (a2-1) copolymer, methacrylate glycidyl / monomer (a2-1) / styrene air. Copolymer, glycidyl methacrylate / monomer (a2-1) / methacrylate tricyclo [5.2.1.O ^2,6 ] decane-8-yl copolymer, glycidyl methacrylate / monomer (a2- 1) / styrene / trimethyl methacrylate [5.2.1.0 ^2,6 ] decane-8-yl copolymer, glycidyl methacrylate / monomer (a2-1) / styrene / cyclohexylmaleimide copolymer, meta Glycidyl acrylate / monomer (a2-1) / styrene / phenylmaleimide copolymer, glycidyl methacrylate / monomer (a2-2) copolymer, glycidyl methacrylate / monomer (a2-2) / Styrene copolymer, glycidyl methacrylate / monomer (a2-2) / tricyclo methacrylate [5.2.1.O ^2,6 ] decane-8-yl copolymer, glycidyl methacrylate / monomer (a2-2) / styrene / methacrylate tricyclo [5.2.1 .0 ^2,6 ] decane-8-yl copolymer, methacrylate glycidyl / monomer (a2-2) / styrene / cyclohexylmaleimide copolymer, methacrylate glycidyl / monomer (a2-2) / Styrene / phenylmaleimide copolymer, etc. are mentioned.

The weight average molecular weight (hereinafter referred to as "Mw") of the copolymer [A] used in the present invention is preferably 2 × 10 ³ to 5 × 10 ⁵ , more preferably 5 × 10 ³ to 1 × 10 ⁵ . If Mw is less than 2x10 <^{3>, the} antihalation film obtained may become inadequate in heat resistance and surface hardness. On the other hand, when it exceeds 5 * 10 <^5> , the flatness of a film surface may become inadequate.

The copolymer [A] used in the present invention is synthesized by radically polymerizing the monomer mixture containing the compound (a1) and the compound (a2) and, if necessary, the compound (a3) in the presence of a polymerization initiator in a solvent. There is a number.

As a solvent used for manufacture of copolymer [A], alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, for example And propylene glycol alkyl ether propionates, aromatic hydrocarbons, ketones, esters and the like.

As these specific examples, For example, methanol, ethanol, etc. as alcohols;

Tetrahydrofuran etc. as ethers;

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc. as glycol ethers;

As ethylene glycol alkyl ether acetates, methyl cellosolve acetate, ethyl cellosolve acetate, etc .;

Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc. as diethylene glycol;

Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like as propylene glycol monoalkyl ethers;

Propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate and the like as propylene glycol alkyl ether acetates;

As propylene glycol alkyl ether propionates, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;

Toluene, xylene and the like as the aromatic hydrocarbons;

Methyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc. as ketones;

As esters, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, and hydroxy Ethyl hydroxy acetate, butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropionate, butyl 3-hydroxypropionate, 2 Methyl hydroxy-3-methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate propyl, butyl butyl acetate, ethoxy acetate, ethoxy acetate, ethoxy acetate, ethoxy acetate Methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, butoxy Ethyl acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 Ethyl ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3- Methyl methoxypropionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy propylpropionate, 3-ethoxypropionate methyl, 3-ethoxypropionate, 3-ethoxypropionate, 3-e Butyl oxypropionate, 3-propoxy methyl propionate, 3-propoxy propionate, 3-propoxy propionate, 3-butyl propoxypropionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-part When acid profile, may be mentioned esters such as butyl-3-butoxy-propionic acid, respectively.

Among these, ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol monoalkyl ethers and propylene glycol alkyl ether acetates are preferable, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and propylene glycol monomethyl Ether and propylene glycol monomethyl ether acetate are preferable.

As a polymerization initiator used for manufacture of copolymer [A], what is generally known as a radical polymerization initiator can be used, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- ( Azo compounds such as 2,4-dimethylvaleronitrile) and 2,2'-azobis- (4-methoxy-2,4-dimethylbarellonitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; And hydrogen peroxide. When using a peroxide as a radical polymerization initiator, it can also be set as a redox type initiator by using a peroxide together with a reducing agent.

In manufacture of copolymer [A], in order to adjust molecular weight, a molecular weight modifier can be used. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan and thioglycolic acid; Xanthogens such as dimethyl xanthogen sulfide and diisopropyl xanthogen disulfide; Tapinene, (alpha) -methylstyrene dimer, etc. are mentioned.

[B] component

The at least 1 sort (s) of compound chosen from the group which consists of [B] polyhydric carboxylic anhydride and polyhydric carboxylic acid used by this invention act as a hardening | curing agent with respect to copolymer [A]. As the component (B), polyhydric carboxylic anhydride is preferable.

As said polyhydric carboxylic acid, aliphatic polyhydric carboxylic acid, alicyclic polyhydric carboxylic acid, and aromatic polyhydric carboxylic acid are mentioned, for example.

Specific examples thereof include, for example, succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, itaconic acid, and the like as aliphatic polyvalent carboxylic acids;

As alicyclic polyhydric carboxylic acids, hexahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, etc .;

Phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 1,2,5,8-naphthalenetetracarboxylic acid, etc. are mentioned as aromatic polyhydric carboxylic acids, respectively. In these, aromatic polyhydric carboxylic acid is preferable from a viewpoint of the heat resistance etc. of the anti-halation film formed, and trimellitic acid is especially preferable at the point that a high anti-halation film is obtained.

As said polyhydric carboxylic anhydride, aliphatic dicarboxylic anhydride, alicyclic polyhydric carboxylic dianhydride, aromatic polyhydric carboxylic anhydride, ester group containing acid anhydride, and unsaturated polycarboxylic dianhydride, and olefinic unsaturated, for example The copolymer with a compound is mentioned.

Specific examples thereof include, for example, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanic anhydride, maleic anhydride, hexahydrophthalic anhydride, and methyltetra anhydride as aliphatic dicarboxylic anhydrides. Hydrophthalic acid, hymic anhydride, and the like;

As an alicyclic polyhydric carboxylic dianhydride, 1,2,3,4- butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, etc .;

Phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic acid anhydride and the like as the aromatic polyhydric carboxylic anhydride;

As ester group containing acid anhydride, ethylene glycol bis anhydride trimellitate, glycerine tris anhydride trimellitate, etc. are mentioned, respectively.

Among these, aromatic polyhydric carboxylic acid anhydride is preferable, and trimellitic anhydride is particularly preferable in that a high anti-halation film is obtained.

As unsaturated polyhydric carboxylic anhydride used for synthesize | combining the copolymer of the said unsaturated polyhydric carboxylic anhydride and an olefinic unsaturated compound, itaconic anhydride, a citraconic anhydride, a maleic anhydride, a cis 1,2, for example 1 or more types of unsaturated polyhydric carboxylic anhydride selected from the group, such as a 3, 4- tetrahydro phthalic anhydride, are mentioned.

Moreover, as an olefinic unsaturated compound used in order to synthesize | combine the copolymer of unsaturated polyhydric carboxylic anhydride and an olefinic unsaturated compound, For example, styrene, p-methylstyrene, p-methoxy styrene, methyl methacrylate, t Butyl methacrylate, methacrylate tricyclo [5.2.1.O ^2,6 ] decane-8-yl, 2-methylcyclohexyl acrylate, phenylmaleimide, cyclohexyl, etc. 1 or more types of compound are mentioned.

The amount of the structural unit derived from the unsaturated polyvalent carboxylic anhydride contained in the copolymer of the unsaturated polyvalent carboxylic anhydride and the olefinically unsaturated compound is preferably 1 to 80% by weight, more preferably 10 to 60% by weight. .

The polystyrene reduced weight average molecular weight of the copolymer of unsaturated polyhydric carboxylic anhydride and olefinically unsaturated compound is preferably 500 to 50,000, more preferably 500 to 10,000.

An unsaturated polyhydric carboxylic anhydride and an olefinic unsaturated compound can be synthesize | combined by the method similar to above-mentioned copolymer [A].

The use ratio of the component [B] is preferably 3 to 30 parts by weight, more preferably 3 to 15 parts by weight based on 100 parts by weight of the copolymer [A]. When the ratio of the component (B) is less than 3 parts by weight, the various resistances of the anti-halation film obtained may be insufficient. On the other hand, when the ratio of component [B] exceeds 30 weight part, the adhesiveness with respect to the board | substrate of the antihalation film obtained may become inadequate.

<Other ingredients>

Although the curable composition of this invention makes the above-mentioned copolymer [A] and [B] components an essential component, it can contain another component as needed. As such another component, an adhesion | attachment adjuvant, a hardening accelerator, surfactant, a ultraviolet absorber, etc. are mentioned, for example.

[Adhesive preparation]

An adhesive aid can be added in order to improve the adhesiveness of the anti-halation film | membrane formed to a board | substrate.

As this adhesion | attachment adjuvant, the functional silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, is used preferably, for example. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxy Silane, (beta)-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned.

The use ratio of the adhesion aid is preferably 30 parts by weight or less, more preferably 0.1 to 25 parts by weight, particularly preferably 1 to 20 parts by weight based on 100 parts by weight of the copolymer [A]. When the use ratio of the adhesion assistant exceeds 100 parts by weight, the heat resistance of the anti-halation film obtained may be insufficient.

[Hardening accelerator]

A hardening accelerator can be added in order to accelerate reaction with copolymer [A] and [B] component. As such a hardening accelerator, the compound which has a heterocyclic structure containing a secondary nitrogen atom or a tertiary nitrogen atom is mentioned, for example.

Specific examples of such compounds include pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, indole, indazole, benzimidazole or isocyanuric acid or derivatives thereof. Among these, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methyl-1- (2'-cyanoethyl) imidazole, 2-ethyl-4-methyl-1- [2 '-(3 ", 5" -diaminotriazinyl) ethyl] imi Preferred imidazole derivatives, such as dazole and benzimidazole, are most preferably 2-ethyl-4-methylimidazole, 4-methyl-2-phenylimidazole and 1-benzyl-2-methylimidazole. Etc. are used.

These compounds can be used individually or in combination of 2 or more types as a hardening accelerator.

The hardening accelerator is preferably used in a proportion of 5 parts by weight or less, more preferably 1 part by weight or less based on 100 parts by weight of the copolymer [A].

[Surfactants]

Surfactant can be added in order to improve the applicability | paintability of a composition.

As such surfactant, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned, for example.

As said nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene dialkyl ester, etc. are mentioned, for example.

As these specific examples, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc. are mentioned as polyoxyethylene alkyl ether, for example, Polyoxyethylene aryl ether is polyoxy; Ethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether are mentioned, Polyoxyethylene dilaurate, polyoxyethylene distearate, etc. are mentioned as polyoxyethylene dialkyl esters.

As a commercial item of such a surfactant, it is a fluorine-type surfactant, a brand name from BMCHIMIE company make: BM-1000, BM-1100, the Dai Nippon Ink Chemical Industries, Ltd. brand name: Megapack F 142 D, copper F 172, copper F 173, East F 183, Sumitomo 3M Co., Ltd. brand name: Florade FC-135, East FC-170 C, East FC-430, East FC-431, Asahi Glass Co., Ltd. brand name: Suflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, Such as SC-106, manufactured by Neos Co., Ltd. Brand Name: DFX-16, DFX-18, DFX-20, etc .;

Toray Dow Corning Silicone Co., Ltd. make as a silicone type surfactant, brand name: SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190, Shin-Etsu Chemical Co., Ltd. (Trade name) KP 341, Shin-Aki Kasei Co., Ltd. brand name: F-Top EF 301, EF 303, EF 352, etc .;

As nonionic surfactant, Kyoeisha Chemical Co., Ltd. make. Brand name: (meth) acrylic acid type copolymer polyflow No. 57, East No. 90, copper No. 95 and the like.

These surfactant can be used individually or in combination of 2 or more types.

Although the use ratio of surfactant changes also with the kind, ratio, etc. of each component which comprises a curable composition, Preferably it is 5 weight part or less with respect to 100 weight part of copolymers [A], More preferably, it is 0.0001-2 weight Parts, more preferably 0.001 to 0.5 parts by weight or less.

Preparation of Thermosetting Compositions

The thermosetting composition of the present invention is dissolved in a suitable solvent and used in solution. For example, the thermosetting composition of a solution state can be manufactured by mixing copolymer [A] and [B] components, and the other component added as needed in a predetermined ratio.

The thermosetting composition of the present invention is prepared by uniformly dissolving or dispersing each component in a suitable solvent. As the solvent used, those which do not react with each component by dissolving or dispersing each component of the composition are used.

As such a solvent, the same thing as what was illustrated as a solvent used at the time of manufacturing copolymer [A] mentioned above can be used. As the usage-amount of a solvent, content of the total solid (copolymer [A] and [B] component and the other components added as needed) in the thermosetting composition of this invention becomes like this. Preferably it is 1-50 weight part, More preferably, Is a range of 5 to 40 parts by weight.

Moreover, a high boiling point solvent can be used together with said solvent. As a high boiling point solvent which can be used together, it is N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpi, for example. Rollidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, dioxalic acid Ethyl, diethyl maleate, (gamma)-butyrolactone, ethylene carbonate, propylene carbonate, a phenyl cellosolve acetate, etc. are mentioned.

As a usage-amount when using a high boiling point solvent together, Preferably it is 90 weight part or less, More preferably, it is 80 weight part or less with respect to exclusive solvent quantity.

The solution of the thermosetting composition prepared as described above may be used after being separated by filtration using a Millipore filter having a pore size of about 0.2 to 3.0 μm, preferably about 0.2 to 0.5 μm, and the like.

Formation method of anti-halation film of solid-state image sensor

Next, the method of forming the anti-halation film of the solid-state image sensor of this invention using the thermosetting composition of this invention is demonstrated.

The method of forming the anti-halation film of the solid-state imaging device of the present invention includes at least the following steps [1] and [2].

[1] forming a coating film of the above-mentioned thermosetting composition on a substrate, and

[2] A step of heat treating the coating film.

Hereinafter, it demonstrates in order.

[1] A step of forming a coating film of the thermosetting composition described above on a substrate.

In the formation method of the anti-halation film of the solid-state image sensor of this invention, the process of first forming the coating film of the thermosetting composition of this invention on a board | substrate is performed. Formation of the coating film on a board | substrate is performed by apply | coating the thermosetting composition of this invention on a board | substrate.

In the present invention, a substrate such as glass, quartz, silicon, or resin can be used as the substrate. As resin, resin, such as a ring-opening polymer of polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, and cyclic olefin, and its hydrogenated substance, is mentioned, for example.

As a coating method, the appropriate method, such as the spray method, the roll coating method, the rotation coating method, the bar coating method, the inkjet method, can be employ | adopted, for example.

Thereafter, the coating film can be formed on the substrate by removing the solvent. In the present invention, there is no need to provide a solvent removal step in particular independently, and may be such that the solvent naturally disperses during the step, and the solvent removal step may be integrated with the following "step of heating the coating film". You can also do it. In addition, it does not exclude employ | adopting a separate solvent removal process. When performing a solvent removal process separately, it can carry out by maintaining a suitable time at the temperature of room temperature to about 150 degreeC.

The thickness of the coating film is preferably 0.1 to 5 mu m, more preferably 0.5 to 3 mu m. This value should also be understood as the film thickness after solvent removal.

[2] heat treatment of coating film

The coating film formed on the board | substrate as mentioned above can be made into the anti-halation film of the solid-state image sensor of this invention by performing a heat processing process continuously.

Heating temperature becomes like this. Preferably it is 150-220 degreeC. Although heating time can be set suitably according to the kind of heating apparatus to be used, etc., it can be set as about 3 to 15 minutes when using a hotplate as a heating apparatus, and about 15 to 30 minutes when using a clean open.

This heat treatment step may be performed in one step or may be performed in a combination of two or more steps.

Anti-halation film of solid-state image sensor

The anti-halation film of the solid-state imaging device of the present invention formed as described above can effectively suppress diffuse reflection light from the base substrate in the exposure step when forming a color filter or microlens on the anti-halation film. It also has a high degree of heat resistance. Therefore, the color filter and microlens formed on the anti-halation film of the solid-state image sensor of this invention can be made into the desired shape and size.

In addition, the thickness of the anti-halation film of a solid-state image sensor becomes like this. Preferably it is 0.1-5 micrometers, More preferably, it is 0.5-3 micrometers.

When this value is less than 0.1 µm, the effect of suppressing diffuse reflection light from the base substrate may be insufficient, while it is not necessary to increase the thickness to more than 5 µm.

Solid-state imaging device

The solid-state image sensor of this invention has the said antihalation film.

Since the color filter and the microlens formed on the anti-halation film are of the desired shape and size, the solid-state imaging device of the present invention is excellent in reliability.

<Example>

Although a synthesis example and an Example are shown to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example.

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 6 parts by weight of 2,2'-azobis (isobutyronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were placed. Subsequently, 17.5 parts by weight of styrene, 77.5 parts by weight of glycidyl methacrylate, and 5 parts by weight of monomer (a2-1) (manufactured by Otsuka Kagaku Co., Ltd., trade name "RUVA-93") were added thereto, followed by nitrogen replacement. Agitation was started. The temperature of the solution was raised to 95 ° C., and the temperature was maintained for 3 hours to obtain a polymer solution containing a copolymer [A-1]. Solid content concentration of the obtained polymer solution was 33.9 weight%, and the polystyrene conversion weight average molecular weight of copolymer [A-1] was 8,500.

Synthesis Example 2

1 part by weight of 2,2'-azobis (isobutyronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer. Subsequently, 70 parts by weight of glycidyl methacrylate and 30 parts by weight of the monomer (a2-1) (manufactured by Otsuka Chemical Co., Ltd., trade name "RUVA-93") were put thereinto, followed by nitrogen substitution, followed by gentle stirring. . The temperature of the solution was raised to 95 ° C, and this temperature was maintained for 3 hours to obtain a polymer solution containing a copolymer [A-2]. Solid content concentration of the obtained polymer solution was 33.0 weight%, and the polystyrene conversion weight average molecular weight of copolymer [A-2] was 20,000.

Synthesis Example 3

2 parts by weight of 2,2'-azobis (isobutyronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer. Subsequently, 10 parts by weight of styrene, 80 parts by weight of glycidyl methacrylate, and 10 parts by weight of monomer (a2-2) were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 95 ° C., and this temperature was maintained for 3 hours to obtain a polymer solution containing a copolymer [A-3]. Solid content concentration of the obtained polymer solution was 33.4 weight%, and the polystyrene conversion weight average molecular weight of copolymer [A-3] was 10,000.

Comparative Synthesis Example 1

2 parts by weight of 2,2'-azobis (isobutyronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene and 80 parts by weight of glycidyl methacrylate were added thereto, followed by nitrogen replacement, followed by gentle stirring. The temperature of the solution was raised to 95 ° C., and this temperature was maintained for 3 hours to obtain a polymer solution containing a copolymer [R-1]. Solid content concentration of the obtained polymer solution was 32.8 weight%, and the polystyrene conversion weight average molecular weight was 10,000.

<Example 1>

An amount corresponding to 100 parts by weight of the copolymer [A-1] (solid content) of the polymer solution containing the copolymer [A-1] synthesized in Synthesis Example 1 was diluted with 100 parts by weight of propylene glycol monomethyl ether acetate. 5 parts by weight of γ-glycidoxypropylethoxysilane as an adhesion aid and 0.075 parts by weight of SH28PA (silicone-based surfactant, manufactured by Toray Dow Corning Silicon Co., Ltd.) as an surfactant, and anhydrous trimelli as [B] component. A thermosetting composition [S-1] was obtained by adding 5 parts by weight of a 25% by weight solution of diethylene glycol methylethyl ether in transic acid in terms of solid content and stirring sufficiently.

Formation of the anti-halation film

The curable composition [S-1] prepared above was apply | coated using the spin coater on the glass substrate, and it heat-processed at 180 degreeC for 3 minutes with the hotplate, and formed the antihalation film of 1.62 micrometer of film thicknesses.

Evaluation of the anti-halation film

(1) light transmittance

The transmittances of 365 nm and 400 nm were measured using a spectrophotometer 150-20 type double beam (manufactured by Hitachi Seisakusho Co., Ltd.) on the substrate having the antihalation film formed as described above. Subsequently, after further heating at 185 degreeC for 20 minutes with a hotplate, the transmittance | permeability of 365 nm and 400 nm was measured similarly. These values are shown in Table 1 below. When the transmittance of 365 nm is 70% or less, it can be said that the antihalation performance, that is, the effect of suppressing diffuse reflection light from the base substrate in the exposure step when forming the color filter or the microlens is excellent. Further, when the transmittance of 400 nm is 95% or more, it can be said that the transmittance of visible light is good.

As to the anti-halation film formed in Example 1, it can be seen that the anti-halation performance and the visible light transmittance are excellent both before and after the additional heating.

(2) heat and moisture resistance

For the substrate having the antihalation film formed as described above, the change in the film thickness before and after treatment for 7 days at 85 ° C.-85% RH in a constant temperature and humidity bath was measured. Table 1 shows the moist heat resistance calculated according to the following equation (1).

Moisture-heat resistance = (film thickness after treatment-film thickness before treatment) / (film thickness before treatment) x 100 (%)

(3) patterning of the microlens material

After apply | coating a microlens material (JSR Corporation make, brand name "MFR-380") using a spinner, on the board | substrate which has the anti-halation film formed as mentioned above on 100 degreeC in advance for 90 second on a hotplate It baked and formed the coating film of 2.5 micrometers in thickness. The obtained coating film was exposed to light at a dose of 2,200 J / m ² with a Nikon Corporation NSR1755i7A reduced projection exposure machine (NA = 0.50, λ = 365 nm) through a pattern mask having a 4.0 μm dot 2.0 μm space pattern. It developed by the shaking immersion method at 23 degreeC with the aqueous solution of the tetramethylammonium hydroxide of the weight% by 1 minute. Subsequently, flowing water was washed with ultrapure water at 23 ° C. for 30 seconds and dried to form a pattern on the anti-halation film on the substrate.

The microlens pattern formed here was observed using the scanning electron microscope (the Hitachi Keisoku Service Co., Ltd. make, model "S-4200"). The shape of the pattern is shown in Table 1. At this time, if the anti-halation performance of the anti-halation film (the ability to suppress the diffuse reflection light from the base substrate) is sufficient, the pattern side surface is formed on the plane as shown in Fig. 1 (a). However, if the antihalation performance is insufficient, the standing wave due to the halation at the time of exposure is affected, so that the pattern side surface is wavy as shown in Fig. 1 (b).

Further, after further heating the substrate having the anti-halation film formed as described above with a hot plate at 185 ° C. for 20 minutes, the microlens pattern was formed on the anti-halation film subjected to the additional heat treatment as described above. Formed. Similarly, the observation result of the pattern shape by an electron microscope was shown in Table 1.

<Examples 2 to 4>

In Example 1, 100 weight part of solutions containing the copolymer shown in Table 1 were added instead of the solution containing copolymer [A-1] as copolymer [A], and [B] The addition amounts of trimellitic anhydride as a component, SH28PA (silicone-based surfactant, manufactured by Toray Dow Corning Silicon Co., Ltd.) and γ-glycidoxypropylethoxysilane as an adhesion aid are shown in Table 1, respectively. It carried out similarly to Example 1 except having performed it.

In addition, trimellitic anhydride which is [B] component is added as a 25 weight% diethylene glycol methyl ethyl ether solution, and the addition amount of [B] component in Table 1 is the amount which converted the solution into solid content. In addition, the film thickness of the anti-halation film formed in each Example is shown in Table 1.

The evaluation results are shown in Table 1.

Example 5

In Example 1, the addition amount of the 25 weight% solution of the diethylene glycol methyl ethyl ether of trimellitic anhydride which is [B] component is 3 weight part in conversion of solid content, and SH28PA (silicone surfactant, Toray Dow which is surfactant) Corning Silicon Co., Ltd.) and the addition amount of (gamma)-glycidoxy propyl ethoxysilane which are adhesion | attachment adjuvant were respectively shown in Table 1, and 0.002 weight of 2-ethyl-4- methylimidazole as an effect promoter It carried out similarly to Example 1 except having added part. In addition, the film thickness of the anti-halation film formed here was 1.62 micrometer.

The evaluation results are shown in Table 1.

<Example 6>

In Example 2, it carried out similarly to Example 2 except having set the addition amount of [B] component 5 weight part, the adhesion | attachment preparation amount 5 weight part, and the addition amount of surfactant to 0.05 weight part. The film thickness of the formed anti-halation film was 0.5 micrometer. The evaluation results are shown in Table 1.

Comparative Example 1

In Example 1, 100 weight part of solutions containing the copolymer [R-1] synthesize | combined by the said comparative synthesis example 1 were added instead of the solution containing copolymer [A-1], and also radiation It carried out similarly to Example 1 except having added 10 weight part of tinuvin 234 (made by Chiba-Geigi Co., Ltd.) as an absorbent. In addition, the film thickness of the anti-halation film formed here was 1.63 micrometers.

The evaluation results are shown in Table 1.

Although the anti-halation performance before the additional heating of the anti-halation film of the comparative example 1 is favorable, it is understood that the anti-halation performance after the additional heating falls remarkably, and heat resistance is inferior.

According to the present invention, in the exposure step when forming a color filter or a microlens in a solid-state image sensor, halides can effectively suppress diffuse reflection light from the base substrate, have high transmittance of visible light, and have high heat resistance. Provided are a thermosetting composition suitable for forming a protective film, a method of forming an anti-halation film using the same, and a solid-state imaging device having the anti-halation film formed by the method and the anti-halation film thereof.

Claims (7)

[A] (a1) an epoxy group-containing unsaturated compound, and (a2) a copolymer of a monomer mixture containing a radically polymerizable compound having a radiation absorbing group, and (B) A thermosetting composition comprising at least one compound selected from the group consisting of polyhydric carboxylic anhydrides and polyhydric carboxylic acids. The thermosetting composition according to claim 1, wherein the radically polymerizable compound having a radiation absorbing group (a2) comprises a structure represented by the following formula (1) as a radiation absorbing group. <Formula 1> The thermosetting composition according to claim 2, wherein (a2) the radically polymerizable compound having a radiation absorbing group is at least one of the compounds represented by the following formulas (2) to (4). <Formula 2> In the formula, R ¹ and R ² are the same or different, and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, a hydroxy group, a halogen atom, a carboxyl group or an alkoxycarbonyl group, and R ³ is An alkylene group having 2 to 10 carbon atoms is represented, and R ⁴ represents a hydrogen atom or a methyl group. <Formula 3> In the formula, the definition of R ⁴ is the same as above, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. <Formula 4> In the formula, the definitions of R ³ , R ⁴ and R ⁵ are the same as described above, and R ⁶ represents an alkylene group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group. The thermosetting composition of any one of Claims 1-3 which is for formation of the anti-halation film of a solid-state image sensor. [1] a step of forming a coating film of the thermosetting composition according to claim 4 on a substrate, and [2] A method of forming an anti-halation film for a solid-state imaging device, comprising at least a step of heating the coating film. The anti-halation film of the solid-state image sensor formed by the method of Claim 5. The solid-state image sensor which has the anti-halation film of Claim 6.