TWI682245B - Radiation-sensitive resin composition, infrared shielding film and forming method thereof, solid-state imaging device, and illumination sensor - Google Patents

Abstract

The radiation-sensitive resin composition regarding the present invention, it is possible to form a film having a high infrared shielding property. The infrared shielding film can be used a solid-state imaging device, the illumination sensor. The radiation-sensitive resin composition contains [A] polymer, [B] quinonediazide compound, and [C] infrared-shielding material.

Description

Radiation-sensitive resin composition, infrared shielding film and its forming method, solid-state imaging element, and illuminance sensor

The invention relates to a radiation-sensitive resin composition, an infrared shielding film, a method for forming the same, a solid-state imaging element, and an illuminance sensor.

Complementary Metal Oxide Semiconductor (CMOS) image sensor chips that are solid-state imaging elements for color images are used in smartphones, cameras, and the like. These solid-state imaging elements use silicon photodiodes that are sensitive to near infrared rays in their light-receiving portions, and therefore require correction of visibility, and therefore use infrared cut filters (for example, refer to Patent Document 1). In addition, an illuminance sensor is installed in a smartphone or the like, and it is used for indoor and outdoor screen brightness adjustment, etc. Therefore, an infrared cut filter is used (for example, refer to Patent Document 2).

However, there is a problem that if the surface of the solid-state imaging element substrate or the like is opposed to the infrared cut filter as described above, the dependence of the incident angle of the solid-state imaging element on the received light becomes large, which becomes malfunction. (Malfunction) cause.

In order to reduce the dependency of the incident angle of the infrared cut filter, attempts have been made to form a curable resin composition film on the substrate (for example, refer to Patent Document 3).

However, it is difficult for these curable resin compositions to form patterns of infrared shielding films with high sensitivity and good patternability. Therefore, from the viewpoint of improving productivity of solid-state imaging elements or illuminance sensors, a radiation-sensitive resin composition that can form a pattern of an infrared shielding film with high sensitivity and excellent patternability is required. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-28620 [Patent Document 2] Japanese Patent Laid-Open No. 2011-60788 [Patent Document 3] Japanese Patent Laid-Open No. 2012-189632

[Problems to be Solved by the Invention] The present invention is based on the above-mentioned facts, and its object is to provide a pattern that can form an infrared shielding film with high sensitivity, and has excellent radiation resistance, high shielding property, chemical resistance, and refractive index. The resin composition provides a solid-state imaging element including an infrared shielding film formed from the radiation-sensitive resin composition, an illuminance sensor, and a method of forming an infrared shielding film. [Technical means to solve the problem]

The invention made to solve the above problems can be achieved by a radiation-sensitive resin composition containing [A] polymer, [B] quinonediazide compound, and [C] infrared shielding material, and further by [A] polymerization The substance is achieved by a polymer having a structural unit containing a carboxyl group and a structural unit containing a crosslinkable group in the same or different polymer molecules.

In addition, another invention made to solve the above problem can be achieved by an infrared shielding film formed of the radiation-sensitive resin composition, a solid-state imaging element or an illuminance sensor including the infrared shielding film. In addition, it can be achieved by a method of forming an infrared shielding film including a step of forming a coating film on a substrate, a step of irradiating at least a portion of the coating film with radiation, and a development of the radiation-irradiated coating film The step and the step of heating the developed coating film form the coating film using the radiation-sensitive resin composition of the present invention. [Effect of invention]

The present invention is based on the facts described above, and its object is to provide a radiation-sensitive resin composition that can form an infrared shielding film with high sensitivity, has excellent infrared shielding properties, chemical resistance, and refractive index. A solid-state imaging element including an infrared shielding film formed from the radiation-sensitive resin composition, an illuminance sensor, and a method of forming an infrared shielding film. An infrared shielding film formed from the radiation-sensitive resin composition, a method for forming the same, and a solid-state imaging element including the infrared shielding film can be provided. Therefore, the radiation-sensitive resin composition, the infrared shielding film, and the method of forming the same can be suitably used in the manufacturing process of solid-state imaging elements, illuminance sensors, and the like.

<Radiation sensitive resin composition> The radiation sensitive resin composition of the present invention is a radiation sensitive resin composition containing [A] polymer, [B] quinonediazide compound, and [C] infrared shielding material. It is not particularly limited if it is a polymer, and from the viewpoint of pattern formation, a polymer having developability is preferred. As a particularly preferred polymer from such a viewpoint, a polymer containing a structural part such as a phenolic hydroxyl group, a carboxyl group, and a silanol group is preferable. Such polymer is preferably acrylic resin, novolak resin, polyamic acid, polyimide, polybenzoxazole, polysiloxane, polyether, etc., particularly preferably selected from acrylic resin, novolac system At least one polymer of resin, polyamic acid, and polyimide. Furthermore, the polymer is particularly preferably a polymer having a structural unit containing a carboxyl group and a structural unit containing a crosslinkable group in the same or different polymer molecules. In addition, the radiation-sensitive resin composition may contain other optional components within a range that does not impair the effects of the present invention. Hereinafter, each component will be described in detail.

<[A] Polymer> The [A] polymer contained in the radiation-sensitive resin composition of the present embodiment is a resin soluble in an alkaline solvent, and is a resin having alkali developability. [A] The polymer is preferably, for example, one selected from acrylic resins having a carboxyl group, polyimide and polyimide precursor, polysiloxane, and novolac resin. Hereinafter, each of the acrylic resin having a carboxyl group, the polyimide resin, the polysiloxane, and the novolac resin will be described in more detail.

[Acrylic resin having a carboxyl group] The acrylic resin having a carboxyl group preferably contains a structural unit having a carboxyl group and a structural unit having a polymerizable group. In this case, if it includes a structural unit having a carboxyl group and a structural unit having a polymerizable group, and has alkali developability (alkali solubility), it is not particularly limited.

The structural unit having a polymerizable group is preferably at least one structural unit selected from the group consisting of a structural unit having an epoxy group and a structural unit having a (meth)acryloyloxy group. When the acrylic resin having a carboxyl group contains the specific structural unit, a film having excellent surface curability and deep curability can be formed, and a cured film according to an embodiment of the present invention can be formed.

The structural unit having a (meth)acryloyloxy group can be formed by, for example, a method of reacting an epoxy group in the copolymer with (meth)acrylic acid, and a carboxyl group in the copolymer having an epoxy group Method for reacting (meth)acrylates, method for reacting hydroxyl groups in copolymers with (meth)acrylates having isocyanate groups, method for reacting acid anhydride sites in copolymers with hydroxyl (meth)acrylates Wait. Among these methods, a method of reacting a carboxyl group in the copolymer with an (meth)acrylate having an epoxy group is particularly preferred.

The acrylic resin containing a structural unit having a carboxyl group and a structural unit having an epoxy group as a polymerizable group may (A1) be selected from at least one group selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter also referred to as "(A1) compound") is synthesized by copolymerizing (A2) an epoxy-containing unsaturated compound (hereinafter also referred to as "(A2) compound"). In this case, the acrylic resin having a carboxyl group becomes a structural unit including at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and an unsaturated compound containing an epoxy group Copolymer of the constituent units.

The acrylic resin having a carboxyl group can be produced by, for example, in a solvent and in the presence of a polymerization initiator, (A1) compound providing a structural unit containing a carboxyl group and (A2 providing a structural unit containing an epoxy group ) Compound copolymerization. Further, (A3) a hydroxyl-containing unsaturated compound (hereinafter also referred to as "(A3) compound") that provides a hydroxyl-containing constituent unit may be further added to make a copolymer. In addition, in the production of the acrylic resin having a carboxyl group, the (A4) compound (provided from the (A1) compound and (A2) may be further added together with the above-mentioned (A1) compound, (A2) compound and (A3) compound ) The unsaturated compound of the structural unit other than the structural unit of the compound and (A3) compound) is made into a copolymer. Next, each compound of (A1) to (A3) will be described in detail.

((A1) Compound) (A1) Compounds include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, and mono[(meth)acryloyloxyalkyl] of polycarboxylic acids. Ester etc.

Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, and crotonic acid.

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid.

Examples of the acid anhydride of the unsaturated dicarboxylic acid include acid anhydrides of the compounds exemplified as the above dicarboxylic acid.

Among these (A1) compounds, acrylic acid, methacrylic acid, and maleic anhydride are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are more preferable from the viewpoint of copolymerization reactivity, solubility in an alkaline aqueous solution, and availability. These (A1) compounds can be used alone or in combination of two or more.

Based on the total of (A1) compound and (A2) compound (optional (A3) compound and (A4) compound as needed), the use ratio of (A1) compound is preferably 5% to 30% by mass, more preferably 10% by mass %～25mass%. By setting the use ratio of the compound (A1) to 5% by mass to 30% by mass, the solubility of the acrylic resin having a carboxyl group in an alkaline aqueous solution can be optimized, and a film with excellent radiation sensitivity can be formed.

((A2) compound) (A2) The compound is an unsaturated compound containing epoxy groups which has radical polymerizability. Examples of the epoxy group include oxetanyl (1,2-epoxy structure) and oxetanyl (1,3-epoxy structure).

Examples of the monomer having an epoxy group include the glycidyl (meth)acrylate, 3-(meth)acryloyloxymethyl-3-ethyloxetane, and (meth)acrylic acid. 3,4-epoxycyclohexyl methyl ester, (meth)acrylic acid-3,4-epoxy tricyclo[5.2.1.0 ^2.6 ]decyl ester, etc.

These (A2) compounds may be used singly or in combination of two or more.

Based on the total of the (A1) compound and the (A2) compound (optional (A3) compound and (A4) compound as needed), the use ratio of the (A2) compound is preferably 5% by mass to 60% by mass, more preferably 10 Mass% ~ 50 mass%. By setting the use ratio of the (A2) compound to 5% by mass to 60% by mass, the cured film of the present embodiment having excellent curability and the like can be formed.

((A3) compound)

(A3) The compound includes (meth)acrylate having a hydroxyl group, (meth)acrylate having a phenolic hydroxyl group, and hydroxystyrene. Examples of acrylates having hydroxyl groups include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate.

Based on the total of (A1) compound, (A2) compound, and (A3) compound (optional (A4) compound as needed), the use ratio of (A3) compound is preferably 1% by mass to 30% by mass, more preferably 5 Mass% ~ 25 mass%.

((A4) Compound) (A4) The compound is not particularly limited if it is an unsaturated compound other than the (A1) compound, (A2) compound, and (A3) compound. (A4) Compounds include, for example, chain alkyl methacrylate, cyclic alkyl methacrylate, chain alkyl acrylate, cyclic alkyl acrylate, aryl methacrylate, and aryl acrylate , Unsaturated dicarboxylic acid diester, maleimide compound, unsaturated aromatic compound, conjugated diene, unsaturated compound with tetrahydrofuran skeleton and other unsaturated compounds, etc.

These (A4) compounds may be used alone or in combination of two or more. The use ratio of the (A4) compound is preferably 10% by mass to 80% by mass based on the total of the (A1) compound, (A2) compound, and (A4) compound (and any (A3) compound).

As specific examples and polymerization methods of these monomers, polymerization can be carried out by a known method. Refer to Japanese Patent No. 2961722, Japanese Patent No. 3241399, Japanese Patent No. 5567364, Japanese Patent No. 3838626, Japanese Patent No. 4853228 , Japanese Patent No. 4947300, Japanese Patent No. 5002275, etc.

<Polyimide and polyimide precursor> Polyimide is preferably a polyimide having an alkali-soluble group in the structural unit of the polymer. Examples of the alkali-soluble group include carboxyl groups. By having an alkali-soluble group, such as a carboxyl group, in the constituent unit, it can have alkali developability (alkali solubility), and suppress the occurrence of scum in the exposed portion during alkali development. Similarly, the polyimide precursor may have an alkali-soluble group such as a carboxyl group and be alkali-soluble.

In addition, if the polyimide has a fluorine atom in the constituent unit, it is preferable to impart water repellency to the interface of the film and suppress the infiltration of the interface during development with an alkaline aqueous solution. The content of fluorine atoms in the polyimide is preferably 10% by mass or more in order to sufficiently obtain the effect of preventing the permeation of the interface, and is preferably 20% by mass or less from the viewpoint of solubility in the alkaline aqueous solution.

The polyimide used in the composition of the present embodiment is, for example, a polyimide obtained by condensation of an acid component and an amine component. The acid component is preferably selected from tetracarboxylic dianhydride, and the amine component is preferably selected from diamine. The tetracarboxylic dianhydride used in the formation of polyimide is preferably 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride Anhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'- Benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1, 1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane Dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl) benzene dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 2, 2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 3,3',4,4'-diphenyl ash tetracarboxylic dianhydride, 9,9-bis(3,4-di Carboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, acid dianhydride having the structure shown below, etc. Two or more of these compounds can also be used.

Specific examples of the diamine used in the formation of polyimide are preferably 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl Ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl Phenyl sulfone, 3,4'-diamino diphenyl sulfone, 4,4'-diamino diphenyl sulfone, 3,3'-diamino diphenyl sulfide, 3,4'-diamine Diphenyl sulfide, 4,4'-diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 1,4-bis(4-aminophenoxy)benzene, 9,9-bis (4-aminophenyl) fluorene, a diamine having the structure shown below, and the like. Two or more of these compounds can also be used.

As such polyimide and polyimide precursor, for example, polymers disclosed in Japanese Patent Laid-Open No. 2011-133699, Japanese Patent Laid-Open No. 2009-258634, etc. can also be used.

[Polysiloxane] If polysiloxane is a polymer of a compound having a siloxane bond, it is not particularly limited. The polysiloxane is usually hardened using, for example, an acid generated by a photo acid generator or a base generated by a photo base generator as a catalyst.

The polysiloxane is preferably a hydrolyzed condensate of a hydrolyzable silane compound represented by the following formula (2B).

[Chemical 1]

In formula (2B), R ²⁰ is a non-hydrolyzable organic group having 1 to 20 carbon atoms. R ²¹ is a C 1-4 alkyl group. q is an integer from 0 to 3. When R ²⁰ or R ²¹ are plural, these groups may be the same or different.

Examples of the non-hydrolyzable organic group having 1 to 20 carbon atoms represented by R ²⁰ include alkyl groups having 1 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 12 carbon atoms. . These groups may be linear, branched, or cyclic. Moreover, some or all of the hydrogen atoms possessed by these alkyl groups, aryl groups, and aralkyl groups may be substituted with vinyl groups, (meth)acryloyl groups, or epoxy groups.

Examples of the C 1-4 alkyl represented by R ²¹ include methyl, ethyl, n-propyl, isopropyl, and butyl. q is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 and 1, and still more preferably 1. When q is the above value, the hydrolysis/condensation reaction becomes easier, and as a result, the rate of the curing reaction becomes higher, and the strength, adhesiveness, and the like of the resulting cured film can be improved.

Among the hydrolyzable silane compounds represented by these formula (2B), silane compounds substituted with 4 hydrolyzable groups and silane compounds substituted with 1 non-hydrolyzable group and 3 hydrolyzable groups are preferred, and more preferred are Silane compound substituted by 1 non-hydrolyzable group and 3 hydrolyzable groups. Specific examples of preferred hydrolyzable silane compounds include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane , Phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-shrink Glyceroloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane. One type of such hydrolyzable silane compounds may be used alone, or two or more types may be used in combination.

The condition for hydrolyzing and condensing the hydrolyzable silane compound represented by the formula (2B) is as long as at least a part of the hydrolyzable silane compound represented by the formula (2B) is hydrolyzed to convert the hydrolyzable group into a silanol group and cause The conditions of the condensation reaction are not particularly limited, and can be carried out as an example as follows.

As the water used in the hydrolysis condensation of the hydrolyzable silane compound represented by the formula (2B), it is preferable to use water purified by methods such as reverse osmosis membrane treatment, ion exchange treatment, and distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved.

The solvent that can be used in the hydrolysis condensation of the hydrolyzable silane compound represented by the formula (2B) is not particularly limited, and examples thereof include ethylene glycol monoalkyl ether acetate and diethylene glycol dialkyl ether. , Propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, propionate esters, etc.

For the polysiloxane, for example, the polysiloxane disclosed in Japanese Patent Laid-Open No. 2011-28225, Japanese Patent Laid-Open No. 2006-178436, and the like can also be used.

<Cyclic olefin-based resin> The cyclic olefin-based resin is not particularly limited as long as it is a resin having a cyclic olefin site, and for example, the cyclic olefin-based resin described in WO2013/054864 can be used. It can be synthesized by the method described.

<Polycarbonate> The polycarbonate is not particularly limited as long as it is a polycarbonate resin containing a fluorene portion, and for example, the polycarbonate described in Japanese Patent Laid-Open No. 2008-163194 can be used.

[Novolak resin] The novolak resin preferred as the resin used in the radiation-sensitive resin composition of the present embodiment can be obtained by making phenols in formalin and other aldehydes by a known method Polycondensation.

Examples of the phenols for obtaining a preferred novolak resin in this embodiment include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, and 2,4-dimethylphenol. , 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2, 3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylene bisphenol, methylene bis-p-cresol, resorcinol, Catechol, 2-methylresorcinol, 4-methylresorcinol, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p Methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, β-naphthol, etc. Two or more of these compounds can also be used.

In addition, as the aldehydes for obtaining a preferred novolak resin in the present embodiment, in addition to formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, etc. may be mentioned. Two or more of these compounds can also be used.

The weight-average molecular weight of the novolak resin preferred as the resin used in the radiation-sensitive resin composition of the present embodiment is preferably 2000 in terms of polystyrene conversion of gel permeation chromatography (GPC). ～50,000, more preferably 3,000～40,000.

<[B] Quinonediazide compound> The [B]quinonediazide compound, which can be contained as a suitable component in the radiosensitive resin composition, generates carboxylic acid by irradiation of radiation. By further containing the [B] quinonediazide compound in the radiation-sensitive resin composition, the radiation-sensitive resin composition can be given a positive radiation-sensitive characteristic in which the exposed portion is removed by the development step.

As the [B] quinonediazide compound, a condensate of a compound having a phenolic hydroxyl group and naphthoquinonediazidesulfonyl halide is preferably mentioned.

Examples of the compound having a phenolic hydroxyl group include compounds represented by the following formula.

[Chem 2]

[Chemical 3]

Among these compounds, as the compound having a phenolic hydroxyl group, 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylene]bis Phenol, 1,1,1-tris(p-hydroxyphenyl)ethane.

Examples of the naphthoquinonediazide sulfonyl halide include 1,2-naphthoquinonediazide-4-sulfonyl chloride and 1,2-naphthoquinonediazide-5-sulfonyl chloride. The ester compound (quinonediazide compound) obtained from 1,2-naphthoquinonediazide-4-sulfonyl chloride has absorption in the region of i-rays (wavelength of 365 nm), so it is suitable for i-ray exposure. On the other hand, the ester compound (quinonediazide compound) obtained from 1,2-naphthoquinonediazide-5-sulfonyl chloride absorbs in a wide range of wavelengths, so it is suitable for exposure in a wide range of wavelengths .

As the [B]quinonediazide compound, 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylene]bisphenol and Condensate of 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,1,1-tris(p-hydroxyphenyl)ethane and 1,2-naphthoquinonediazide-5-sulfonyl chloride Of condensates.

The Mw of the [B] quinonediazide compound is preferably 300 to 1,500, and more preferably 350 to 1,200. When the Mw of the [B] quinonediazide compound is 300 or more, the transparency of the formed interlayer insulating film can be maintained high. On the other hand, by setting the Mw of the [B] quinonediazide compound to be 1,500 or less, it is possible to suppress a decrease in the pattern formability of the radiation-sensitive resin composition.

[B] The quinonediazide compound can be used alone or in combination of two or more. The content of [B] quinonediazide compound in the radiation-sensitive resin composition is preferably 1 part by mass to 100 parts by mass, and more preferably 5 parts by mass relative to 100 parts by mass of the polymer component [A]. 50 parts by mass. When the content of the [B] quinonediazide compound is in the above-mentioned specific range, the difference between the solubility of the irradiated portion and the unirradiated portion with respect to the alkaline aqueous solution as the developer becomes large, and as a result, the patterning performance becomes good. Furthermore, the solvent resistance of the obtained interlayer insulating film also becomes good.

[C] Infrared shielding material As the infrared shielding material used in the present invention, if it is a compound that absorbs light with a wavelength of 800 nm to 1200 nm, it can be used without particular limitation, and it can be a metal oxide, copper compound, infrared Any of absorbing dyes and infrared absorbing pigments. The so-called "shielding" refers to blocking a certain part of the space from the influence of an external force field such as an electric field or magnetic field. The so-called "infrared shielding material" refers to a compound that has an effect of blocking the influence of infrared rays.

Among the metal oxides used in the present invention, the infrared shielding material is more preferably the following, from the viewpoint of resolution and sensitivity in pattern formation using a light source with a wavelength of 500 nm or less, and infrared light, and from the viewpoint of resolution and sensitivity. The tungsten compound or metal boride described is most preferably a tungsten compound. The tungsten compound is an infrared shielding material that has high absorption of infrared rays (light with a wavelength of about 800 nm to 1200 nm) (that is, high shielding ability to infrared rays) and low absorption of visible light. Therefore, since the curable composition for a solid-state imaging element of the present invention contains a tungsten compound, it not only has high shielding properties in the infrared region, but also can form a pattern with high sensitivity.

Examples of the tungsten compound include tungsten oxide compounds, tungsten boride compounds, and tungsten sulfide compounds. More preferred are tungsten oxide compounds represented by the following general formula (I) (composition formula). MxWyOz (I) M represents metal, W represents tungsten, and O represents oxygen. 0.001≦x/y≦1.1 ≦2.2≦z/y≦3.0

Examples of the metal of M include alkali metals, alkaline earth metals, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga , In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, preferably alkali metals. The metal of M may be one kind, or two or more kinds.

Preferably M is an alkali metal, preferably Rb or Cs, and more preferably Cs. By making x/y more than 0.001, infrared rays can be shielded sufficiently, and by making it 1.1 or less, it is possible to more reliably avoid the formation of impurity phases in tungsten compounds. By making z/y 2.2 or more, the chemical stability of the material can be further improved, and by making it 3.0 or less, infrared rays can be shielded sufficiently.

Specific examples of the tungsten oxide-based compound represented by the general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO ₃ and the like, preferably Cs _0.33 WO ₃ or Rb _0.33 WO ₃ , more preferably Cs _0.33 WO ₃ .

The tungsten compound is preferably fine particles. The average particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and still more preferably 200 nm or less. By setting the average particle diameter to such a range, it becomes difficult for tungsten fine particles to block visible light due to light scattering, so that the light transmittance in the visible light region can be made more reliable. From the viewpoint of avoiding light scattering, the smaller the average particle diameter is, the more preferable. However, the average particle diameter of the tungsten fine particles is usually 1 nm or more for reasons such as ease of handling during manufacturing.

The tungsten compound can be obtained as a commercially available product, but when the tungsten compound is, for example, a tungsten oxide-based compound, the tungsten oxide-based compound can be obtained by heat-treating the tungsten compound in an inert gas environment or a reducing gas environment Method (refer to Japanese Patent No. 4096205). Furthermore, tungsten oxide compounds can also be obtained as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

Like tungsten compounds, metal borides have high absorption of infrared light (wavelength of about 800 nm to 1200 nm), low absorption of visible light, and exposure to high-pressure mercury lamps, KrF, ArF, etc. used in image formation The wavelength used in is shorter than the visible region and the absorption of light is also small. Therefore, if the curable composition for a solid-state imaging element of the present invention contains a metal boride, as in the case of containing a tungsten compound, high shielding properties in the infrared region, high transparency in the visible region, and excellent resolution and sensitivity can be obtained. picture of.

Examples of the metal boride include lanthanum boride (LaB ₆ ), boride boride (PrB ₆ ), neodymium boride (NdB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), and titanium boride (TiB ₂ ), zirconium boride (ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), molybdenum boride One or more of (MoB ₂ , Mo ₂ B ₅ , MoB), tungsten boride (W ₂ B ₅ ), etc., more preferably lanthanum boride (LaB ₆ ).

The metal boride is preferably fine particles. The average particle diameter of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and still more preferably 100 nm or less. When the average particle diameter is in such a range, it becomes difficult for the metal boride fine particles to block visible light due to light scattering, so that the light transmittance in the visible light region can be made more reliable. From the viewpoint of avoiding light scattering, the smaller the average particle diameter, the more preferable. However, the average particle diameter of the metal boride fine particles is usually 1 nm or more for reasons such as ease of handling during manufacturing.

The metal boride can be obtained as a commercially available product, and can also be obtained as a dispersion of metal boride fine particles such as KHF-7 manufactured by Sumitomo Metal Mining Co., Ltd., for example.

The copper compound used in the present invention is not particularly limited if it has a maximum absorption wavelength in the range of 700 nm to 1200 nm (near infrared region). The copper compound used in the present invention may or may not be a copper complex, preferably a copper complex. When the copper compound used in the present invention is a copper complex, the ligand L coordinated to copper is not particularly limited as long as it can form a coordinate bond with copper ions, and examples thereof include sulfonic acid and phosphoric acid. , Phosphate, phosphonic acid, phosphonate, phosphinic acid, phosphinate, carboxylic acid, carbonyl (ester, ketone), amine, amide, sulfonamide, carbamate, urea, alcohol, sulfur Alcohol and other compounds. Among these compounds, sulfonic acid, phosphoric acid, phosphoric acid ester, phosphonic acid, phosphonic acid ester, phosphinic acid and phosphinic acid ester are preferable, and sulfonic acid, phosphoric acid ester, phosphonic acid ester and phosphinic acid ester are more preferable. As specific examples of the copper compound used in the present invention, a copper compound containing phosphorus, a copper sulfonate compound, a copper carboxylate compound, or a copper compound represented by the following general formula (A) is more preferable. As a phosphorus-containing compound, the compound described in WO2005/030898 can be specifically referred to, and these contents are incorporated in the specification of the present application. The copper phosphate compound used in the present invention will be described in detail below.

The composition of the present invention preferably contains a copper phosphate compound and an antioxidant. The composition of the present invention contains a copper phosphate compound, preferably 20 to 95% by mass relative to the solid content of the composition, and more preferably 30 to 80% by mass. The copper phosphate compound may be one kind or two or more kinds, and in the case of two or more kinds, the total amount is within the above range.

The copper phosphate compound used in the present invention is preferably formed using a phosphate compound, and more preferably formed using a compound represented by the following formula (II). Formula (II) (HO) _n -P(=O)-(ORa ² ) _3-n (In the formula, Ra ² represents an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and 1 carbon atom ~18 aralkyl group, or C1-C18 alkenyl group, -ORa ² represents C4-C100 polyoxyalkyl group, C4-C100 (meth)acryloyloxyalkyl group , Or (meth)acryloyl polyoxyalkyl having 4 to 100 carbon atoms, n represents 1 or 2. When n is 1, Ra ² may be the same or different)

In the above formula, it is preferred that at least one of -ORa ² represents a (meth)acryloyloxyalkyl group having 4 to 100 carbon atoms, or a (meth)acryloyloxyalkylene group having 4 to 100 carbon atoms. The group is more preferably a (meth)acryloyloxyalkyl group having 4 to 100 carbon atoms. Polyoxyalkyl having 4 to 100 carbon atoms, (meth)acryloyloxyalkyl having 4 to 100 carbon atoms, or (meth)acryloylpolyoxyalkyl having 4 to 100 carbon atoms The carbon number is preferably 4-20, and more preferably 4-10. In formula (II), Ra ² is preferably a C 1-18 alkyl group, a C 6-18 aryl group, more preferably a C 1-10 alkyl group, a C 6-10 aryl group, Even more preferably, it is an aryl group having 6 to 10 carbon atoms, and particularly preferably a phenyl group. In the present invention, when n is 1, one of Ra ² is -ORa ² , preferably representing (meth)acryloyloxyalkyl having 4 to 100 carbon atoms or (meth) having 4 to 100 carbon atoms. Radical) acrylamide polyoxyalkyl, and the other of Ra ² is -ORa ² or preferably alkyl.

Furthermore, examples of the phosphate compound of the present invention include phosphate monoesters (n=2 in the formula (II)) and phosphate diesters (n=1 in the formula (II)), but from near infrared rays From the viewpoints of shielding properties and solubility, phosphodiester is preferred.

The copper phosphate complex is in the form of a copper complex (copper compound) in which phosphate is coordinated to copper as the central metal. The copper in the phosphate copper complex is divalent copper. For example, a copper salt can be reacted with a phosphate ester to produce it. Therefore, if it is a near-infrared absorption composition containing copper and a phosphate compound, it can be predicted that a copper phosphate complex is formed in the composition.

The molecular weight of the copper phosphate compound used in the present invention is preferably 300 to 1500, and more preferably 320 to 900.

As a specific example of the phosphate compound, reference may be made to the description of Japanese Patent Laid-Open No. 2001-354945, and these contents are incorporated in the specification of the present application. In addition, regarding the synthesis method, preferred examples, and the like of the copper phosphate compound used in the present invention, reference may be made to the description of International Publication No. WO99/26952, and the contents of this specification are incorporated into the specification of the present application. In the synthesis of copper phosphate compounds, commercially available products such as Phosmer M, Phosmer PE, Phosmer PP (Uni-Chemical) Co., Ltd.) and other phosphonic acids.

The infrared absorbing dye that can be used as an infrared shielding material in the present invention is selected from the group consisting of cyanine pigments, phthalocyanine pigments, naphthalocyanine pigments, ammonium pigments, ammonium pigments, quinolinium pigments, pyranium pigments, and Ni-co Compound pigment, pyrrolopyrrole pigment, copper complex, tetralin pigment, azo pigment, anthraquinone pigment, diimmonium pigment, squarylium pigment and porphyrin pigment At least one of the groups. The pigment that can be used as an infrared shielding material in the present invention can also be obtained as a commercially available product. For example, the following commercially available pigments can be suitably cited.

S0345, S0389, S0450, S0253, S0322, S0585, S0402, S0337, S0391, S0094, S0325, S0260, S0229, S0447, S0378, S0306, S0484 manufactured by FEW Chemicals Source, Inc.) manufactured ADS795WS, ADS805WS, ADS819WS, ADS820WS, ADS823WS, ADS830WS, ADS850WS, ADS845MC, ADS870MC, ADS880MC, ADS890MC, ADS920MC, ADS990MC, ADS805PI, ADSW805PP, ADS810CO, ADS813MT, ADS815A, ADS815MT, ADS815A , ADS821NH, ADS822MT, ADS838MT, ADS840MT, ADS905AM, ADS956BP, ADS1040P, ADS1040T, ADS1045P, ADS1040P, ADS1050P, ADS1065A, ADS1065P, ADS1100T, ADS1120F

YKR-4010, YKR-3030, YKR-3070, MIR-327, MIR-371, SIR-159, PA-1005, MIR-369, MIR-379, SIR-128, PA-1006 manufactured by Yamamoto Chemical Co., Ltd. , YKR-2080, MIR-370, YKR-3040, YKR-3081, SIR-130, MIR-362, YKR-3080, SIR-132, PA-1001 NK-123, NK-124 manufactured by the Linyuan Institute of Biochemistry , NK-1144, NK-2204, NK-2268, NK-3027, NKX-113, NKX-1199, NK-2674, NK-3508, NKX-114, NK-2545, NK-3555, NK-3509, NK -3519

As specific examples of the cyanine-based dye and the perylene triphenyl-based dye, compounds described in Japanese Patent Laid-Open No. 2012-215806, Japanese Patent Laid-Open No. 2008-009206, and the like can be cited. Specific examples of the phthalocyanine compound include Japanese Patent Laid-Open No. 60-224589, Japanese Patent Laid-Open No. 2005-537319, Japanese Patent Laid-Open No. 4-23868, Japanese Patent Laid-Open No. 4-39361 , Japanese Patent Laid-Open No. 5-78364, Japanese Patent Laid-Open No. 5-222047, Japanese Patent Laid-Open No. 5-222301, Japanese Patent Laid-Open No. 5-222302, Japanese Patent Laid-Open No. 5-345861 , Japanese Patent Laid-Open No. 6-25548, Japanese Patent Laid-Open No. 6-107663, Japanese Patent Laid-Open No. 6-192584, Japanese Patent Laid-Open No. 6-228533, Japanese Patent Laid-Open No. 7-118551 , Japanese Patent Laid-Open No. 7-118552, Japanese Patent Laid-Open No. 8-120186, Japanese Patent Laid-Open No. 8-225751, Japanese Patent Laid-Open No. 9-202860, Japanese Patent Laid-Open No. 10-120927 , Japanese Patent Laid-Open No. 10-182995, Japanese Patent Laid-Open No. 11-35838, Japanese Patent Laid-Open No. 2000-26748, Japanese Patent Laid-Open No. 2000-63691, Japanese Patent Laid-Open No. 2001-106689 The compounds described in Japanese Patent Laid-Open No. 2004-18561, Japanese Patent Laid-Open No. 2005-220060, and Japanese Patent Laid-Open No. 2007-169343.

Hereinafter, as specific examples of the azo dye, the anthraquinone dye (anthraquinone compound), and the squarylium-based dye (squaraine compound), the compounds described in Japanese Patent Laid-Open No. 2012-215806 and the like can be cited.

The pigment can also be obtained as a commercially available product, for example, Lumogen IR765, Lumogen IR788 (made by BASF); ABS643, ABS654, ABS667, ABS670T, IRA693N, IRA735 (excited (Made by Exciton); SDA3598, SDA6075, SDA8030, SDA8303, SDA8470, SDA3039, SDA3040, SDA3922, SDA7257 (manufactured by HWANDS); TAP-15, IR-706 (manufactured by Yamada Chemical Industries) In particular, cyanine pigments may be Daito chmix 1371F (manufactured by Daito Chemix), phthalocyanine pigments may include Excolor series, Excolor TX-EX 720, and Excolor ) 708K (manufactured by Japanese catalyst company), etc., but not limited to this.

These pigments may be used alone, or two or more of these pigments corresponding to the purpose may be mixed and used in order to show good shielding properties.

Examples of the infrared absorbing pigment that can be used as an infrared shielding material in the present invention include zinc white, lead white, zinc barium white, titanium oxide, chromium oxide, iron oxide, settleable barium sulfate, barite powder, and lead red , Iron oxide red, chrome yellow, zinc yellow (zinc potassium chromate, zinc tetraoxychromate), ultramarine blue, Prussian blue (ferrous ferrocyanide), zircon gray, zirconium yellow, chrome titanium yellow, Chrome green, peacock blue, Victoria green, iron blue (not related to Prussian blue), vanadium zirconium blue, chrome tin red, manganese red, orange red, titanium black, tungsten compound, metal boride, etc. In addition, black pigments can be used Metal oxides, metal nitrides or mixtures of one or more metal elements of one or more metal elements free from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag.

The content of the infrared shielding material is preferably 0.1% by mass or more and 50% by mass or less, and more preferably 1% by mass or more and 45% by mass or less relative to the mass of all solid components of the curable composition for a solid-state imaging device of the present invention. It is even more preferably 5% by mass or more and 40% by mass or less, and most preferably 5% by mass or more and 20% by mass or less. Moreover, two or more infrared shielding materials can be used.

<Other optional components> The radiation-sensitive resin composition may further contain a photoacid generator (other than quinonediazide compounds), an antioxidant, a polyfunctional acrylate, and a surface as needed within the range that does not impair the effects of the present invention. Other optional components such as active agents, adhesion aids, inorganic oxide particles, compounds having a cyclic ether group, and solvents. Other arbitrary components may be used alone or in combination of two or more.

<Acid generator (except quinonediazide compounds)> It is preferable that the acid generator of the present invention generate an acid with a pKa of 3 or less by irradiating actinic rays or radiation. The acid generator may also be a compound that can generate acid due to heat. Examples of the acid generated from the acid generator by irradiation with actinic rays or radiation include carboxylic acid, sulfonic acid, phosphoric acid, sulfinic acid, sulfuric acid, sulfurous acid, sulfuric acid monoester, hydrochloric acid, hexafluorophosphoric acid, and tetrafluoroboric acid Wait for the fourth grade boric acid. Examples of the acid-generating compound include organic halogenated compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, and onium salt compounds.

Specific examples of the organic halogenated compound include Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), US Patent No. 3,905,815, and Japanese Patent Publication No. 46-4605 , Japanese Patent Publication No. 48-36281, Japanese Patent Publication No. 55-32070, Japanese Patent Publication No. 60-239736, Japanese Patent Publication No. 61-169835, Japanese Patent Publication No. 61-169837 , Japanese Patent Publication No. 62-58241, Japanese Patent Publication No. 62-212401, Japanese Patent Publication No. 63-70243, Japanese Patent Publication No. 63-298339, MP Hutt, " The compounds described in the Journal of Heterocyclic Chemistry (Jurnal of Heterocyclic Chemistry), 1 (No3), (1970), particularly include oxazole compounds substituted with trihalomethyl groups: s-triazine compounds. More preferably, at least one mono-, di-, or tri-halogen substituted methyl group is bonded to the s-triazine ring, and specific examples thereof include: 2,4,6-tris (monochloromethyl) -S-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6- Bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, etc.

Examples of organic boron compounds include Japanese Patent Laid-Open No. 62-143044, Japanese Patent Laid-Open No. 62-150242, Japanese Patent Laid-Open No. 9-188685, Japanese Patent Laid-Open No. 9-188686, Japanese Patent Laid-Open No. 9-188686 9-188710, Japanese Patent Laid-Open No. 2000-131837, Japanese Patent Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent No. 2000-310808 and other bulletins, as well as Kunz, Martin, and Radiation Curing (RadTech) 98, Proceeding (Proceeding) April 19 to 22, 1998, the organic borate described in Chicago, etc., Japanese Patent Laid-Open No. 6-157623, Japanese Patent Laid-Open No. 6-175564, Japan The organoboron sulfonium complex or organoboron oxysulfonium complex described in Japanese Patent Laid-Open No. 6-175561, Japanese Patent Laid-Open No. 6-175554, and Japanese Patent Laid-Open No. 6-175553 Organoboronium iodonium complex described, organoborophosphonium complex described in Japanese Patent Laid-Open No. 9-188710, Japanese Patent Laid-Open No. 6-348011, Japanese Patent Laid-Open No. 7-128785 , Japanese Patent Laid-Open No. 7-140589, Japanese Patent Laid-Open No. 7-306527, Japanese Patent Laid-Open No. 7-292014, etc. described in organoboron transition metal coordination complexes and the like.

Examples of the disulfonic acid compound include compounds described in Japanese Patent Laid-Open No. 61-166544, Japanese Patent Laid-Open No. 2002-328465, and the like.

As the oxime ester compound, there may be cited the Journal of the British Chemical Society, Pulkin Journal II (JCS Perkin II) (1979) 1653-1660, and the Journal of the British Chemical Society, Pulkin Journal II (JCS Perkin II) (1979) 156-162 The compounds described in Journal of Photopolymer Science and Technology (1995) 202-232 and Japanese Patent Laid-Open No. 2000-66385 are preferably sulfonates from the viewpoint of sensitivity.

Examples of the onium salt compound include SI Schlesinger (SI Schlesinger), Photographic Science and Engineering (Photographic Science and Engineering, Photogr. Sci. Eng.), 18, 387 (1974), and TS Bal (TS Bal ) Et al., Polymer (Polymer), Diazonium salt described in 21,423 (1980), Ammonium salt described in US Patent No. 4,069,055, Japanese Patent Laid-Open No. 4-365049, etc., US Patent Phosphonium salts described in the specifications of US Patent No. 4,069,055, US Patent No. 4,069,056, European Patent No. 104,143, US Patent No. 339,049, US Patent No. 410,201, Japanese Patent Laid-Open No. 2-150848, The iodonium salt described in Japanese Patent Laid-Open No. 2-296514, European Patent No. 370,693, European Patent No. 390,214, European Patent No. 233,567, European Patent No. 297,443, European Patent No. 297,442, and U.S. Patent No. 4,933,377 No., U.S. Patent No. 161,811, U.S. Patent No. 410,201, U.S. Patent No. 339,049, U.S. Patent No. 4,760,013, U.S. Patent No. 4,734,444, U.S. Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, The sulfonium salts described in the specifications of German Patent No. 3,604,581, JV Crivello et al., Macromolecules, 10(6), 1307 (1977), JV Crivello ( JV Crivello et al., selenium salt described in Polymer Science Journal, Polymer Chemistry Edition (J. PolymerSci., PolymerChem. Ed.), 17, 1047 (1979), CS Wen (CS Wen) et al., Zheng (Teh), Proc. Conf. Rad. Curing ASIA, p. 478, onium salts such as arsenium salts described in Tokyo, October (1988).

Particularly from the viewpoint of reactivity and stability, the acid generator is preferably the oxime ester compound or the onium salt compound. Examples of the onium salt compound include diazonium salts, iodonium salts, and sulfonium salts.

It is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less, and even more preferably 0.1% by mass with respect to the total solid content of the radiation-sensitive resin composition of the present invention. % Above 15% by mass.

Antioxidants include phenol-based antioxidants, sulfur-based antioxidants, and amine-based antioxidants. Phenolic antioxidants are particularly preferred. Antioxidants can be used alone or in combination of two or more. The content of the antioxidant is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the total [A] polymer component contained in the radiation-sensitive resin composition of the present embodiment, and particularly preferably 0.2 Mass parts ~ 5 parts by mass. By using within this range, the heat resistance of the infrared shielding film formed from the radiation-sensitive resin composition can be further improved.

As the antioxidant, the antioxidant described in Japanese Patent Laid-Open No. 2011-227106 and the like can be used.

The polyfunctional acrylate is 100 parts by mass or less, preferably 0.1 parts by mass or more and 80 parts by mass or less, more preferably 0.5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polymer component [A]. More preferably, it is 1 mass part or more and 25 mass parts or less. By using within this range, the heat resistance and solvent resistance of the infrared shielding film formed of the radiation-sensitive resin composition can be further improved.

As the polyfunctional acrylate, the polyfunctional acrylate described in Japanese Patent Laid-Open No. 2005-227525 and the like can be used.

The surfactant is a component that improves the formability of the coating film of the radiation-sensitive resin composition. Since the radiation-sensitive resin composition contains a surfactant, the surface smoothness of the coating film can be improved. As a result, the film thickness uniformity of the infrared shielding film formed of the radiation-sensitive resin composition can be further improved.

The adhesion aid is a component that improves the adhesion between the film forming object such as a substrate and the infrared shielding film. The adhesion aid is especially used to improve the adhesion between the inorganic substrate and the infrared shielding film. The adhesion aid is preferably a functional silane coupling agent.

As the inorganic oxide particles, the following inorganic oxide particles can be used. The inorganic oxide particles contain a group selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium, and hafnium. Oxide of at least one element. The inorganic oxide particles described in Japanese Patent Laid-Open No. 2011-128385 can be used.

The compound having a cyclic ether group is a compound having a cyclic ether group and different from the polymer contained in the polymer component [A]. Since this radiation-sensitive resin composition contains a compound having a cyclic ether group, the thermal reactivity of the compound having a cyclic ether group can be used to promote cross-linking of [A] the polymer component, etc. The hardness of the infrared shielding film formed by the resin composition can improve the radiation sensitivity of the radiation-sensitive resin composition.

The compound having a cyclic ether group is preferably a compound having two or more epoxy groups (oxepropyl group and oxetanyl group) in the molecule. As the compound having a cyclic ether group and the compound having an epoxy group, the compounds described in Japanese Patent Laid-Open No. 2011-257537 can be used.

Among these compounds, the compound having a cyclic ether group is preferably a compound having two or more oxetanyl groups in the molecule, and more preferably bis[(3-ethyloxetan-3- Group) methyl] ester, 1,4-bis[(3-ethyloxetan-3-yl)methoxymethyl]benzene, 2,2-bis(hydroxymethyl)-1-butan 1,2-epoxy-4-(2-oxepropyl) cyclohexane adduct of alcohol (EHPE3150 (made by Daicel Chemical Co., Ltd.)).

The content of the compound having a cyclic ether group is usually 150 parts by mass or less relative to 100 parts by mass of the polymer component [A], preferably 0.5 parts by mass or more and 100 parts by mass or less, and more preferably 1 part by mass or more , 50 parts by mass or less, and more preferably 10 parts by mass or more and 25 parts by mass or less. By setting the content of the compound having a cyclic ether group to the above range, the hardness of the infrared shielding film formed of the radiation-sensitive resin composition can be further increased.

<Preparation method of radiation-sensitive resin composition> The radiation-sensitive resin composition can be prepared by combining [A] polymer, [B] quinonediazide compound, and [C] infrared shielding material with solvents as appropriate The components and other arbitrary components are mixed to prepare a dissolved or dispersed state. For example, the radiation-sensitive resin composition can be prepared by mixing the components in a predetermined ratio in a solvent.

<Solvent> As the solvent, a solvent that uniformly dissolves or disperses other components in the radiation-sensitive resin composition and does not react with the other components can be suitably used. Examples of such a solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propylene glycol. Monoalkyl ether propionate, aromatic hydrocarbons, ketones, other esters, etc. As the solvent, the solvent described in Japanese Patent Laid-Open No. 2011-232632 can be used.

<Polymer composition> The polymer composition of the present invention contains a polymer component having a first structural unit containing an acid dissociable group, a second structural unit containing a crosslinkable group, and a At least one group of structural units. The polymer component is the same as the [A] polymer component of the radiation-sensitive resin composition.

<Infrared shielding film> The infrared shielding film of the present invention is formed from the radiation-sensitive resin composition. The infrared shielding film is formed of the radiation-sensitive resin composition, and therefore has excellent water repellency, appearance characteristics of the coating film, and uniformity of the film thickness. The infrared shielding film having such characteristics can be suitably used as an infrared shielding film such as a solid-state imaging element, an illuminance sensor, and a proximity sensor (proximity sensor). In addition, the method of forming the infrared shielding film is not particularly limited, and the method of forming the infrared shielding film described below is preferably applied.

<Method of Forming Infrared Shielding Film> The radiation-sensitive resin composition can be suitably used in the formation of an infrared shielding film.

The method for forming an infrared shielding film of the present invention includes a step of forming a coating film on a substrate using the radiation-sensitive resin composition (hereinafter also referred to as "step (1)"), and at least Part of the step of irradiating radiation (hereinafter also referred to as "step (2)"), the step of developing the coating film irradiated with radiation (hereinafter also referred to as "step (3)"), and the developed coating film The step of heating (hereinafter also referred to as "step (4)").

This method of forming an infrared shielding film can form an infrared shielding film with high pattern shape stability. Furthermore, the amount of change in film thickness of the unexposed portion can be suppressed, and as a result, the process margin of production can be increased, and the yield can be improved. In addition, by forming patterns using photosensitive exposure, development, and heating, an infrared shielding film having a fine and delicate pattern can be easily formed.

[Step (1)] In this step, the radiation-sensitive resin composition is applied on the substrate to form a coating film. When the radiation-sensitive resin composition contains a solvent, the solvent is preferably removed by prebaking the coated surface.

Examples of the substrate include glass, quartz, silicone, and resin. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, and cyclic olefin ring-opening polymers and their hydrogenated products. . The conditions of the pre-baking vary depending on the types of ingredients, the mixing ratio, etc., and are usually 70°C to 120°C for about 1 minute to 10 minutes.

[Step (2)] In this step, at least a part of the coating film is irradiated with radiation and exposed. At the time of exposure, exposure is usually performed through a mask screen having a predetermined pattern. The radiation used for exposure is preferably radiation having a wavelength in the range of 190 nm to 450 nm, and more preferably radiation containing ultraviolet light at 365 nm. The exposure amount is preferably 500 J/m ² to 6,000 J/m ² , and more preferably 1,500 J/m ² to 1,800 J/m ² . The exposure amount is a value measured by an illuminance meter ("OAI model 356" of Optical Associates Inc., OAI) of the intensity of radiation at a wavelength of 365 nm.

[Step (3)] In this step, the coating film irradiated with radiation is developed. By developing the exposed coating film, unnecessary portions (irradiated portions) can be removed to form a predetermined pattern.

As the developer used in this step, an alkaline aqueous solution is preferred. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Furthermore, as a developer containing an organic solvent, an organic solvent such as a ketone-based organic solvent or an alcohol-based organic solvent can also be used. By using such a developing solution containing an organic solvent, negative and positive reverse patterns can be formed (for example, refer to Japanese Patent Laid-Open No. 2014-199272).

It can also be used by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution. The concentration of the alkali in the alkaline aqueous solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of obtaining suitable developability.

Examples of the development method include a coating method, a dipping method, a shaking dipping method, and a spray method. The development time varies depending on the composition of the radiation-sensitive resin composition, and is usually about 10 seconds to 180 seconds. Following this development treatment, for example, 30-90 seconds of running water washing is performed, and then it is air-dried with, for example, compressed air or compressed nitrogen, whereby a desired pattern can be formed. The rate of change in the film thickness after development relative to the film thickness of the coating film before development is preferably 90% or more. If the formation method using the radiation-sensitive resin composition is used as described above, the amount of change in film thickness of the unexposed portion with respect to the development time can be suppressed, and the film thickness after development can be maintained as before the development More than 90% of the film thickness.

[Step (4)] In this step, the developed coating film is heated. A heating device such as a hot plate or an oven is used for heating. By heating the patterned film, the curing reaction of the polymer component [A] can be promoted to form an infrared shielding film. The heating temperature is, for example, about 120°C to 250°C. The heating time varies depending on the type of heating equipment, for example, it is about 5 minutes to 30 minutes for a hot plate, and about 30 minutes to 90 minutes for an oven. Furthermore, a step baking method or the like that performs two or more heating steps can also be used. As described above, a patterned thin film corresponding to the target infrared shielding film can be formed on the surface of the substrate. The film thickness of the infrared shielding film is preferably 0.1 μm to 8 μm, and more preferably 0.1 μm to 6 μm.

<Solid-state imaging element> FIG. 1 is a schematic cross-sectional view showing the configuration of a camera module including a solid-state imaging element. The camera module 200 shown in FIG. 1 is connected to a circuit board 70 as a package board via solder balls 60 as connection members. In detail, the camera module 200 is composed of the following components: a solid-state imaging element substrate 100 having an imaging element portion on the first main surface of the silicon substrate, and a first main surface side (light-receiving side) provided on the solid imaging element substrate 100 A planarization layer (a film not shown in FIG. 1 and having under 42), a glass substrate 30 (translucent substrate) disposed above the infrared shielding film provided on the planarization layer, and a glass substrate 30 The internal space above the substrate 30 includes a lens holder 50 of the imaging lens 40 and a light-shielding and electromagnetic shielding material 44 arranged so as to surround the solid-state imaging element substrate 100 and the glass substrate 30. Each member is adhered with an adhesive (not shown in FIG. 1). The present invention is a method of manufacturing a camera module including a solid-state imaging element substrate and an infrared shielding film disposed on the light-receiving side of the solid-state imaging element substrate, by applying the radiation-sensitive radiation of the present invention on the light-receiving side of the solid-state imaging element substrate Resin composition to form an infrared shielding film. Therefore, in the camera module of the present embodiment, for example, the infrared shielding film is formed by applying the radiation-sensitive resin composition of the present invention to the planarization layer. The method of forming the infrared shielding film is as described above. In the camera module 200, incident light hν from the outside sequentially passes through the imaging lens 40, the glass substrate 30, the near-infrared cut filter 42, and the planarization layer 46, and then reaches the imaging element portion of the solid-state imaging element substrate 100. In addition, the camera module 200 is connected to the circuit board 70 via the solder ball 60 (connecting material) on the second main surface side of the solid-state imaging element substrate 100.

<Illumination Sensor> The configuration of the illuminance sensor of this embodiment will be described with reference to FIG. 2. 2 is a cross-sectional view showing the configuration of an illuminance sensor. As shown in the figure, the illuminance sensor includes a glass epoxy substrate 4, an illuminance sensor light receiving element 6, a distance detecting light receiving element 8, an infrared light emitting element 10, a gold wire 12, a resin 16, and an infrared shielding film 18. The illuminance sensor 1 detects the distance by injecting infrared rays emitted from the infrared light emitting element 10 and reflected to the object into the light receiving element 8 for distance detection. In addition, the illuminance sensor unit 2 includes a glass epoxy resin substrate 4, an illuminance sensor light-receiving element 6, a gold wire 12, a resin 16, and an infrared shielding film 18. [Example]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. [A] The weight average molecular weight (Mw) of the polymer component can be measured by the following method.

[Weight Average Molecular Weight (Mw)] Under the following conditions, it was measured by gel permeation chromatography (Gel Permeation Chromatography, GPC). Device: Showa Denko's "GPC-101" column: Combined with GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 Mobile phase: Tetrahydrofuran column temperature: 40°C Flow rate : 1.0 mL/min Sample concentration: 1.0% by mass Sample injection volume: 100 μL Detector: Differential refractometer Reference material: Monodisperse polystyrene

<Synthesis of [A] polymer component> [Synthesis Example 1] (Synthesis of polymer (A-1)) 8 parts by mass of 2,2'-azobis(2 , 4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether. Next, 13 parts by mass of methacrylic acid, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of α-methyl-p-hydroxystyrene, 10 parts by mass of styrene, and 12 parts by mass of tetrahydrofurfuryl methacrylate were charged , 15 parts by mass of N-cyclohexylmaleimide and 10 parts by mass of n-lauryl methacrylate, after nitrogen substitution, while slowly stirring, the temperature of the solution was raised to 70°C, and the temperature was kept at 5 Polymerization is carried out in hours, thereby obtaining a solution containing polymer (A-1). The Mw of the polymer (A-1) is 8000.

[Synthesis Example 2] (Synthesis of polymer (A-2)) Under dry nitrogen flow, 29.30 g (0.08 mole) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane (CENTRAL (CENTRAL GLASS), 1.24 g (0.005 mol) 1,3-bis(3-aminopropyl)tetramethyldisilaxane, 3.27 g (0.03 mol) 3-aminophenol as a blocking agent (Tokyo Chemical Industry Co., Ltd.) dissolved in 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as "NMP"). To this was added 31.2 g (0.1 mole) of bis(3,4-dicarboxyphenyl) ether dianhydride (MANAC) and 20 g of NMP, and the reaction was carried out at 20°C for 1 hour, followed by 50 The reaction was carried out at 4°C for 4 hours. Thereafter, 15 g of xylene was added, and the water and xylene were azeotropically stirred at 150° C. for 5 hours. After the stirring was completed, the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and dried in a vacuum dryer at 80° C. for 20 hours to obtain a polymer (A-2) having a structure represented by the following formula.

[Chemical 4]

[Synthesis Example 3] (Synthesis of polymer (A-3)) In a container equipped with a stirrer, 20 parts by mass of propylene glycol monomethyl ether was charged. Next, 50 parts by mass of methyltrimethoxysilane, 30 parts by mass of phenyltrimethoxysilane, and 20 parts by mass of γ-glycidoxypropyltrimethoxysilane were charged, and the solution was heated until the temperature of the solution became 60°C. After the solution temperature reached 60°C, 0.15 parts by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were charged, and heated to 75°C for 4 hours. Further, the temperature of the solution was set to 40°C, and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol due to hydrolysis and condensation. By the above operation, polysiloxane as a hydrolyzed condensate is obtained as a polymer (A-3). The Mw of the polysiloxane polymer (A-3) was 5,000.

<Synthesis Example of Copper Phosphate Complex> To 50 g (0.38 mol) of 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 73.6 g (0.42 mol) of phenyl phosphate (Tokyo Chemical Industry) To the pyridine solution (180 mL manufactured by Wako Pure Chemical Industries, Ltd.), 116 g (0.38 mol) 1,3,5-triisopropylsulfonyl chloride (Tokyo Chemical Industry Co., Ltd.) was added below 5°C Co., Ltd.) pyridine solution (400 mL). After the addition, the reaction was completed by stirring at room temperature for 6 hours. After adding 2.9 L of a 10% aqueous solution of sodium bicarbonate so that the temperature does not rise above 30° C., washing with ethyl acetate is performed. Concentrated hydrochloric acid was added to the water layer to make the pH 1 and the target substance was extracted with ethyl acetate. After the solvent was distilled off, chloroform/moisture liquid was carried out in order to remove 1,3,5-triisopropyl sulfonic acid by-produced in the reaction. Finally, 10 mg of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the solvent of the organic layer was distilled off, thereby obtaining a phosphate compound (22 g, yield 20%). The phosphate ester (3.15 g, 11.0 mmol) and methanol (16.6 g) were mixed to prepare a methanol solution of the phosphate ester. Copper acetate (1 g, 5.5 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) was added to the methanol solution of the phosphate ester, and the temperature was raised to 50° C. to carry out the reaction for 2 hours. After the reaction was completed, the produced acetic acid and solvent were distilled off by an evaporator, thereby obtaining copper phosphate complex 1 (3.5 g).

[Preparation of Radiation Sensitive Resin Composition] The following shows [B] quinonediazide compounds, [C] infrared shielding materials, and other arbitrary compounds used in the preparation of radiation sensitive resin compositions.

([A] polymer) A-1: polymer (A-1) obtained in Synthesis Example 1 A-2: polymer (A-2) obtained in Synthesis Example 2 A-3: obtained in Synthesis Example 3 Polymer (A-3) A-4: novolak resin (trade name, XPS-4958G, m-cresol/p-cresol ratio = 55/45 (weight ratio), Qunrong Chemical Industry Co., Ltd.) ([B ]Quinonediazide compounds) B-1: 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylene]bisphenol and 1,2-naphthoquinonediazide-5-sulfonyl chloride condensate B-2: 1,1,1-tris(p-hydroxyphenyl)ethane and 1,2-naphthoquinonediazide-5- Sulfochloride condensate

([C] Infrared shielding material) C-1: 18.5 mass% dispersion liquid of YMF-02 (Cesium Tungsten Oxide (Cs _0.33 WO ₃ (average dispersion particle diameter less than 800 nm) manufactured by Sumitomo Metal Mining Co., Ltd.) ) C-2: Anthocyanin pigment (Daito chmix 1371F, maximum absorption wavelength (λmax=805 nm) manufactured by Daito Chemix) C-3: The copper phosphate complex Copper phosphate complex obtained in synthesis 1

([D] compound having a cyclic ether group) D-1: bis[(3-ethyloxetane-3-yl)methyl isophthalate represented by the following formula (D-1) ] Ester D-2: 1,4-bis[(3-ethyloxetan-3-yl)methoxymethyl]benzene represented by the following formula (D-2)

[Chem 5]

([F]Antioxidant) F-1: Pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Adeka’s "Adikes" Adekastab AO-60")

[Preparation of Radiation Sensitive Resin Composition 1] In a polymer solution containing (A-1) as a polymer component [A] (amount equivalent to 100 parts by mass (solid content) of polymer (A-1)) Among them, 25 parts by mass of [B] quinonediazide compound (B-1), 18 parts by mass of [C] infrared shielding material (C-1), 5 parts by mass of [D] having cyclic ether Radiation-sensitive resin composition 1 (hereinafter also referred to as "composition 1") was prepared by (D-1) of the base compound and 0.5 parts by mass of [F] antioxidant (F-1).

[Preparation of Radiation Sensitive Resin Composition 2] In the polymer solution containing (A-2) as the polymer component [A] (amount equivalent to 100 parts by mass (solid content) of polymer (A-2)) In, mixing 30 parts by mass of [B] quinonediazide compound (B-2), 30 parts by mass of [C] infrared shielding material (C-2), 5 parts by mass of [D] having cyclic ether Based compound (D-2), a radiation-sensitive resin composition 2 (hereinafter also referred to as "composition 2") was prepared.

[Preparation of Radiation Sensitive Resin Composition 3] In a polymer solution (equivalent to 100 parts by mass (solid content) of polymer (A-3)) containing polymer (A-3) as a polymer component [A] In the amount), mix 25 parts by mass of [B] quinonediazide compound (B-1), 20 parts by mass of [C] infrared shielding material (C-3), and 1 part by mass of antioxidant (F -1), prepare a radiation-sensitive resin composition 3 (hereinafter also referred to as "composition 3").

[Preparation of Radiation Sensitive Resin Composition 4] In 100 parts by mass of polymer (A-4) as the [A] polymer component, 35 parts by mass of [B] quinonediazide compound (B-1) was mixed ), 20 parts by mass of [C] infrared shielding material (C-3), and 1 part by mass of antioxidant (F-1), to prepare a radiation-sensitive resin composition 4 (hereinafter also referred to as “composition 4”) ).

In the comparative example, the (C-1) compound was not included in the preparation of the radiation-sensitive resin composition 1, and the preparation was carried out in the same manner (hereinafter also referred to as "comparative composition 1").

<Evaluation> The radiation-sensitive resin composition 1 to the radiation-sensitive resin composition 4 and the radiation-sensitive resin composition of the comparative example were used to evaluate radiation sensitivity, infrared shielding property, and chemical resistance of the infrared shielding film. Example 5 was evaluated in the same manner except that the radiation-sensitive resin composition 1 was used and butyl acetate was used in the developer. In the case of Example 5, the unexposed portion was developed with butyl acetate to obtain a pattern in the exposed portion. The evaluation results are shown in Table 1.

[Evaluation of Radiation Sensitivity] The radiation-sensitive resin composition was applied on a silicon substrate using a spinner, and then pre-baked at 90°C on a hot plate for 2 minutes to form a coating film with a thickness of 25.0 μm. Next, using an exposure machine (Canon's "MPA-600FA" (ghi-ray mixing)), exposure was performed through a mask screen having a square island-like pattern of 200 μm, and the coating film was irradiated with the exposure amount set as a variable radiation. Thereafter, in a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 23° C., development was performed by a coating method for 80 seconds. Next, ultrapure water was used for running water for 1 minute, and then dried to form a pattern. At this time, the amount of exposure required to completely dissolve the 200 μm square island pattern was investigated. When the value of this exposure amount is 300 mJ/cm ² or less, it can be judged that the radiation sensitivity is good. The evaluation criteria are shown below. A: Less than 300 mJ/cm ² B: More than 300 mJ/cm ² and less than 400 mJ/cm ²

[Evaluation of Infrared Shielding Property] After applying the radiation-sensitive resin composition on the glass substrate using a spinner under the above conditions, a photosensitive layer (curable composition layer) coating film with a film thickness of 25 μm was formed and spectroscopic was used A photometer ("150-20 type double beam" manufactured by Hitachi, Ltd.) measures the transmittance of the coating film at a wavelength of 1200 nm. The lower the value, the better the infrared shielding property. If the transmittance is 2% or less, it can be said that it has practically good infrared shielding properties.

[Evaluation of Chemical Resistance of Infrared Masking Film] The evaluation of chemical resistance of infrared masking film is swelling due to the peeling liquid. The radiation-sensitive resin composition was applied on a silicon substrate using a spinner, and then pre-baked at 90°C on a hot plate for 2 minutes to form a coating film with a film thickness of 25.0 μm. Next, an oven heated to 230°C was used for sintering for 30 minutes to form an infrared shielding film. This film was immersed in an N-methylpyrrolidone solvent heated at 40° C. for 3 minutes, and the rate of change (%) in film thickness before and after immersion was determined as an index of chemical resistance. Let the film thickness change rate be A: the film thickness change rate is less than 5%, B: the film thickness change rate is 5% or more and less than 10%, C: the film thickness change rate is 10% or more and less than 15%, in A or In the case of B, the chemical resistance was evaluated as good. The film thickness was measured at 25° C. using an optical interference type film thickness measuring device (Lambda ACE VM-1010).

[Evaluation of Refractive Index (Light Refractive Index)] Regarding the substrate having the infrared shielding film formed in the evaluation of chemical resistance, the refractive index was measured by Metricon's "Prism Coupler Model 2010". The refractive index was measured at three wavelengths of 408 nm, 633 nm, and 828 nm. Regarding the refractive index, the case where the measured value at 633 nm was 1.60 or more was evaluated as "A", and the case where it was less than 1.600 was evaluated as "B". When the refractive index is high, it can be said that it is good from the viewpoint of optical characteristics.

[Table 1]

From the results of Table 1, it is understood that the radiation-sensitive resin compositions of Examples 1 to 4 are excellent in radiation sensitivity, and are excellent in infrared shielding properties, chemical resistance, and refractive index. On the contrary, it can be seen that the radiation-sensitive resin composition of the comparative example is excellent in radiation sensitivity and chemical resistance, but has poor infrared shielding properties and refractive index.

1‧‧‧Illuminance sensor 2‧‧‧Illuminance sensor 4‧‧‧Glass epoxy resin substrate (substrate) 6‧‧‧Illuminance sensor light receiving element 8‧‧‧Receiver for distance detection 10‧‧‧Infrared light emitting element (light emitting element) 12‧‧‧Gold thread 16‧‧‧Resin 18‧‧‧Infrared shielding film 30‧‧‧Glass substrate 40‧‧‧Camera lens 42‧‧‧Infrared shielding film/Near infrared cut filter 44‧‧‧Shading and electromagnetic shielding material 50‧‧‧Lens holder 60‧‧‧solder ball 70‧‧‧ circuit board 100‧‧‧Solid imaging element substrate 200‧‧‧Camera module

FIG. 1 is a schematic diagram showing the configuration of a camera module including a solid-state imaging element according to an embodiment of the present invention. 2 is a schematic diagram showing the configuration of an illuminance sensor according to an embodiment of the present invention.

30‧‧‧Glass substrate

40‧‧‧Camera lens

42‧‧‧Infrared shielding film/Near infrared cut filter

44‧‧‧Shading and electromagnetic shielding material

50‧‧‧Lens holder

60‧‧‧solder ball

70‧‧‧ circuit board

100‧‧‧Solid imaging element substrate

200‧‧‧Camera module

Claims (9)

A radiation-sensitive resin composition comprising: [A] polymer, [B] quinonediazide compound, and [C] infrared shielding material, the [C] infrared shielding material contains tungsten oxide cesium, and is selected from copper At least one of compounds, cyanine pigments, phthalocyanine pigments, tetralin pigments, ammonium pigments, imino pigments, azo pigments, anthraquinone pigments, diimmonium pigments, squarylium pigments, porphyrin pigments, The content of the tungsten cesium oxide is 5% by mass or more and 70% by mass or less with respect to the total solid content of the radiation-sensitive resin composition. The radiation-sensitive resin composition as described in item 1 of the patent application scope, the [A] polymer is selected from acrylic resins having a carboxyl group, polyamic acid, polyimide resin, polysiloxane and phenolic At least one polymer in the varnish resin. According to the radiation-sensitive resin composition described in item 1 of the patent application range, the copper compound is a phosphorus-containing compound. The radiation-sensitive resin composition as described in item 1 of the patent application, the selected from the group consisting of copper compounds, cyanine pigments, phthalocyanine pigments, tetralin pigments, ammonium pigments, ammonium pigments, azo pigments, The content of at least one of the anthraquinone pigment, the diimmonium pigment, the squarylium pigment, and the porphyrin pigment is 1% by mass or more and 30% by mass or less with respect to the total solid content of the radiation-sensitive resin composition . An infrared shielding film formed using the radiation-sensitive resin composition according to any one of claims 1 to 4 of the patent application. A solid-state imaging element, as described in item 5 of the patent application scope Infrared shielding film. An illuminance sensor including an infrared shielding film as described in item 5 of the patent application. A method for forming an infrared shielding film, comprising: (1) a step of forming a coating film of a radiation-sensitive resin composition according to any one of claims 1 to 4 on a substrate, (2 ) The step of irradiating at least a part of the coating film formed in step (1), (3) the step of developing the coating film irradiated with radiation in step (2), and (4) the step of (3) ) In the step of heating the developed coating film. In the method for forming an infrared shielding film as described in item 8 of the patent application range, in the step (2), a developer containing an organic solvent is used.

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