TW202007720A - Photosensitive composition, infrared light-cutting filter, and solid-state imaging device - Google Patents

Abstract

Provided are the following: a photosensitive composition which can form a pattern that is excellent in terms of squareness of a cross sectional shape and which can form a cured film having excellent heat resistance; an infrared-cutting filter, and a solid-state imaging device. This photosensitive composition contains metal-containing tungsten oxide particles, a polymerizable compound, a polymerization initiator, an ultraviolet radiation absorber and a polymerization inhibitor. The mass ratio of the content of the ultraviolet radiation absorber relative to the content of the polymerization inhibitor is 0.08-330.

Description

Photosensitive composition, infrared cut filter, solid-state imaging element

The invention relates to a photosensitive composition, an infrared cut filter and a solid-state imaging element.

Solid-state imaging elements that use color images in video cameras, digital cameras, and mobile phones with camera functions. These solid-state imaging devices use silicon photodiodes that are sensitive to infrared rays (infrared light) in their light-receiving parts. Therefore, luminosity correction is required and infrared cut-off filters are often used. Patent Document 1 discloses a photosensitive composition containing predetermined tungsten oxide and/or composite tungsten oxide as a composition for forming an infrared light cut filter. [Prior Technical Literature] [Patent Literature]

[Patent Literature 1] International Publication No. 2011/067998

When forming a pattern using a photosensitive composition, it is required that the cross-sectional shape of the pattern is excellent in rectangularity. In addition, it is required that the cured film formed using the photosensitive composition hardly change the transmittance even after the heat treatment. In particular, even in the case where various color filters are arranged adjacent to the cured film, it is expected that the above-mentioned change in transmittance is unlikely to occur after the heat treatment is performed. Hereinafter, the case where the transmittance is difficult to change after the heat treatment is referred to as excellent heat resistance. The present inventors evaluated the above-mentioned characteristics using the photosensitive composition described in Patent Document 1, and as a result, the characteristics of both could not be satisfactorily satisfied.

In view of the above circumstances, the object of the present invention is to provide a photosensitive composition capable of forming a pattern with excellent rectangularity in cross-sectional shape and capable of forming a cured film having excellent heat resistance. In addition, an object of the present invention is to provide an infrared light cut filter formed using a photosensitive composition and a solid-state imaging element including the infrared light cut filter.

The present inventors have conducted intensive studies on the problems of the conventional technology, and as a result, they have found that the above-mentioned problems can be solved by the following configuration.

(1) A photosensitive composition containing metal-containing tungsten oxide particles, a polymerizable compound, a polymerization initiator, an ultraviolet absorber, and a polymerization inhibitor, in the photosensitive composition The mass ratio of the content of the ultraviolet absorber to the content of the polymerization inhibitor is 0.08 to 330. (2) The photosensitive composition according to (1), wherein the surface of the metal-containing tungsten oxide particles is coated with metal oxide. (3) The photosensitive composition according to (2), wherein the metal oxide is an oxide containing at least one kind of element selected from the group consisting of Si, Ti, Zr, and Al. (4) The photosensitive composition according to any one of (1) to (3), wherein the ultraviolet absorber has a mass reduction rate at 150°C of 5% or less and at 220°C in thermal mass measurement The ultraviolet absorbing agent whose mass reduction rate is more than 40%. (5) The photosensitive composition according to any one of (1) to (4), wherein the ultraviolet absorber is at least one selected from the group consisting of dibenzoylmethane-based compounds and aminobutadiene-based compounds . (6) The photosensitive composition according to any one of (1) to (5), which contains two or more kinds of polymerization inhibitors. (7) The photosensitive composition according to (6), wherein the polymerization inhibitor is selected from the group consisting of hindered phenol compounds, hindered phenol compounds, phenol compounds, benzoquinone compounds, and hydroquinone compounds At least two of them. (8) The photosensitive composition according to (7), wherein the polymerization inhibitor includes one or more first polymerization inhibitors selected from the group consisting of hindered phenol compounds, benzoquinone compounds, and hydroquinone compounds Phenolic compounds other than agents and hindered phenolic compounds. (9) The photosensitive composition according to (8), wherein the mass ratio of the content of the phenolic compound other than the hindered phenolic compound to the total content of the first polymerization inhibitor is 0.0009 to 0.17. (10) The photosensitive composition according to any one of (1) to (9), further including an alkali-soluble binder having a double bond group. (11) An infrared light cut filter formed using the photosensitive composition described in any one of (1) to (10). (12) A solid-state imaging element including the infrared light cut filter described in (11). [Effect of the invention]

According to the present invention, it is possible to provide a photosensitive composition capable of forming a pattern with excellent cross-sectional rectangularity and capable of forming a cured film having excellent heat resistance. In addition, according to the present invention, it is also possible to provide an infrared light cut filter formed using a photosensitive composition and a solid-state imaging element including the infrared light cut filter.

Hereinafter, preferred aspects of the photosensitive composition, infrared cut filter, and solid-state imaging element of the present invention will be described in detail. In the label of the group (atomic group) in this specification, the label which is not described as substituted and unsubstituted includes those without a substituent, and also includes those with a substituent. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). In this specification, "~" is used with the meaning including the numerical value described before and after it as a lower limit value and an upper limit value. In this specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylate" means acrylic and methacrylic, and "(meth)acryl" means acrylic. Group and methacrylic group. In addition, in this specification, "single body" and "monomer" have the same meaning. Monomers are different from oligomers and polymers, and refer to compounds with a weight average molecular weight of 2,000 or less. In this specification, a polymerizable compound refers to a compound having a polymerizable functional group, and may be a single substance or a polymer. The polymerizable functional group refers to a group participating in a polymerization reaction. In this specification, "total solid content" refers to the total mass of components after removing the solvent from all the components of the composition. The solid content in the present invention is a solid content at 25°C.

First, as a characteristic point of the present invention, the point of adjusting the mass ratio of the ultraviolet absorber to the polymerization inhibitor can be mentioned. It was found that by adjusting the above-mentioned mass ratio within a predetermined range, it is possible to balance heat resistance and pattern rectangularity (rectangularity of the formed pattern) with a more excellent balance.

The photosensitive composition contains metal-containing tungsten oxide particles, a polymerizable compound, a polymerization initiator, an ultraviolet absorber, and a polymerization inhibitor. Hereinafter, each component included in the photosensitive composition (hereinafter, also simply referred to as "composition") will be described in detail.

(Tungsten oxide particles containing metal) Tungsten oxide particles containing metal (hereinafter, also referred to as "specific particles") are tungsten oxide particles containing metal atoms. The specific particles selectively block infrared light (light with a wavelength of about 800-1200 nm) according to the crystal structure, and thus have an effect as an infrared absorber. Therefore, the infrared light cut filter including specific particles has high light-shielding property in the infrared region and high light permeability in the visible light region. In addition, the specific particles also have a smaller absorption of short-wavelength light than the visible region used in the exposure of high-pressure mercury lamps, KrF, and ArF used in image formation. Therefore, as described later, the photosensitive composition of the present invention has excellent pattern formability and can finely control the shape of the infrared light cut filter.

The type of metal atoms contained in the specific particles is not particularly limited, and from the viewpoint of more excellent infrared light shielding properties, alkali metals can be cited. The specific particles are preferably represented by the following general formula (composition formula) (I). M _x W _y O _z (I) M represents alkali metal, W represents tungsten, and O represents oxygen. 0.001≤x/y≤1.1 2.2≤z/y≤3.0

The alkali metal of M may be one kind or two or more kinds. As the alkali metal of M, Rb or Cs is preferable, and Cs is more preferable. When x/y is 0.001 or more, infrared light can be sufficiently blocked, and when it is 1.1 or less, it is possible to further avoid generation of an impurity phase in specific particles. When z/y is 2.2 or more, the chemical stability as a material can be further improved, and if it is 3.0 or less, infrared light can be further blocked.

Specific examples of the alkali metal-containing specific particles represented by the general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ and the like, and Cs _0.33 WO ₃ or Rb _0.33 WO ₃ are preferred Yes, Cs _0.33 WO ₃ is even better.

From the viewpoint that the effect of the present invention is more excellent, it is preferable that the surface of the metal-containing tungsten oxide particles be coated with metal oxide. That is, the photosensitive composition preferably contains metal-containing tungsten oxide particles and metal oxide-coated particles arranged so as to cover the surface of the metal-containing tungsten oxide particles. The type of metal oxide is not particularly limited, and oxides containing at least one element selected from the group consisting of Si, Ti, Zr, and Al are preferred. The metal oxide may be arranged to cover the entire surface of the metal-containing tungsten oxide particles, or may be arranged to cover a part of it.

The average particle size of the specific particles is not particularly limited, but it is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. If the average particle diameter is in the above range, it is difficult for specific particles to block visible light due to light scattering, and therefore, the light transmittance in the visible light region is more excellent. From the viewpoint of avoiding light scattering, the smaller the average particle diameter, the better. However, for ease of handling during manufacturing and the like, the average particle diameter of the specific particles is preferably 1 nm or more. In addition, as a method of measuring the average particle diameter, a particle diameter (diameter) of at least 50 specific particles is measured using a known electron microscope (for example, a transmission electron microscope), and these are arithmetically averaged. In addition, when the specific particle is not a true circle, the long diameter is measured as the particle diameter.

The content of specific particles in the photosensitive composition is not particularly limited, but from the viewpoint of more excellent infrared light shielding properties, it is preferably 1 to 20% by mass relative to the total mass of the photosensitive composition, and 3 to 15 Quality% is better. In addition, two or more types of specific particles can be used. In this case, the total content is preferably in the above range.

The specific particles can be obtained as a commercially available product, and can be obtained by heat-treating a tungsten compound containing an alkali metal in an inert gas atmosphere or a reducing gas atmosphere (see Japanese Patent No. 4096205). Also, for example, it can be obtained as a dispersion of fine particles of tungsten oxide containing alkali metal, such as YMF-02A, YMS-01A-2, and YMF-10A-1 manufactured by Sumitomo Metal Mining Co., Ltd.

(Polymerizable compound) As the polymerizable compound, any compound can be used as long as it has a polymerizable group (a group that reacts with at least one of acid, radicals, and heat) in the molecule, and has a plural number in the molecule A multifunctional polymerizable compound with one polymerizable group is preferred. Examples of the polymerizable compound having a polymerizable group that reacts under the action of at least any one of acid, radical, and heat include unsaturated ester functional groups (for example, acryloyl and methacryloyl) , Unsaturated amide group, vinyl ether group and allyl and other ethylenic unsaturated group-containing ethylenically unsaturated group-containing compound; methylol compound; bis-cis-butadiene diimide compound; benzocyclobutene compound ; Diallyl Nadic amide imine compounds; benzo 㗁𠯤 compounds and so on.

The polymerizable compound may be a monomer or a polymer. As the polymerizable compound, a radical polymerizable compound is preferred, and a compound having an ethylenically unsaturated double bond is more preferred. Examples of the polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid, etc.), esters and amides thereof. Saturated carboxylic acid esters, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, or amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds are preferred. In particular, the ester of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound can exhibit high hydrophobicity in the exposed portion, so that it is easy to form a pattern having a desired shape by alkali development, and high durability can be obtained. The pattern is preferred from the viewpoint. In addition, examples of the polymerizable compound include addition reactants of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amine groups, and mercapto groups, and monofunctional or polyfunctional isocyanates or epoxy compounds. In addition, examples of the polymerizable compound include a dehydration condensation reaction product of the above-mentioned unsaturated carboxylic acid ester or amide and a monofunctional or polyfunctional carboxylic acid.

Examples of the unsaturated carboxylic acid ester include methacrylate, itaconic acid ester, crotonic acid ester, isocrotonic acid ester and maleic acid ester.

As the polymerizable compound, a urethane-based addition polymerizable compound produced by the addition reaction of isocyanate and hydroxyl group is also preferable, and specific examples thereof include, for example, Japanese Patent Publication No. 48-041708 A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule is described. The vinyl urethane is represented by the following general formula (E) The vinyl monomer having a hydroxyl group is added to a polyisocyanate compound having two or more isocyanate groups in one cent. CH ₂ =C(R ⁴ )COOCH ₂ CH(R ⁵ )OH(E) [wherein R ⁴ and R ⁵ each independently represent H or CH ₃ . 〕

The number of ethylenically unsaturated double bonds in the radical polymerizable compound is not particularly limited. From the viewpoint of curing sensitivity, two or more are preferable, three or more are more preferable, and four or more are still more preferable . The upper limit is not particularly limited, but there are many cases of 10 or less.

In addition, from the viewpoint of curing sensitivity and developability of the unexposed portion, as the polymerizable compound, a polymerizable compound containing an EO (ethylene oxide) modified body is preferable. In addition, from the viewpoint of curing sensitivity and intensity of the exposed portion, a compound containing a urethane bond is preferred as the polymerizable compound. In addition, from the viewpoint of developability at the time of pattern formation, the polymerizable compound is preferably a compound having an acid group.

Examples of the polymerizable compound include bisphenol A diacrylate, bisphenol A diacrylate EO modified form, trimethylolpropane triacrylate, and trimethylolpropane tris(acryloxypropyl) ether. , Trimethylolethane triacrylate, tetraethylene glycol diacrylate, neopentyl alcohol diacrylate, neopentyl alcohol triacrylate, neopentyl alcohol tetraacrylate, di neopentyl alcohol tetraacrylate Ester, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, Tris(acryloyloxyethyl)isocyanurate, neopentyl tetraol tetraacrylate EO modified body, dipentaerythritol hexaacrylate EO modified body, tricyclodecane dimethanol diacrylate, etc. . Among them, bisphenol A diacrylate EO modified body, neopentaerythritol triacrylate, neopentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri( Acryloyloxyethyl) isocyanurate, neopentaerythritol tetraacrylate EO modified form or dipentaerythritol hexaacrylate EO modified form is preferred.

Further, as commercially available products, urethane oligomers UAS-10, UAB-140 (above manufactured by Sanyo Kokusaku Pulp Co., Ltd.), KAYARAD RP-1040, DPHA-40H, KAYARAD RP can be mentioned. -1040, KAYARAD DPHA, KAYARAD DPCA-20 (above manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, DCP-A (Above manufactured by KYOEISHA CHEMICAL Co., LTD.), NK Ester A-BPE-20, A-DCP, NK Ester A-TMMT, NK Ester A-DPH-12E (above is Shin-Nakamura Chemical Co., Ltd. Manufacturing), TO-756, TO-1382, M-305, ARONIX M-510 (above manufactured by TOAGOSEI CO., LTD.) and OGSOL EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd.).

The content of the polymerizable compound in the photosensitive composition is not particularly limited, but from the viewpoint that the intensity of the infrared light cut filter is more excellent, it is preferably 1 to 20% by mass relative to the total mass of the photosensitive composition. 3 to 10% by mass is better. The polymerizable compound may be used alone or in combination of two or more. Among them, from the viewpoint of more excellent pattern rectangularity, it is preferable to use two or more kinds.

(Polymerization initiator) Examples of the polymerization initiator include photopolymerization initiators and thermal polymerization initiators, and photopolymerization initiators are preferred. In addition, the photopolymerization initiator is a compound which has the ability to initiate polymerization by being sensitive to light, and is preferably sensitive to ultraviolet to visible light. The thermal polymerization initiator is a compound having the ability to initiate polymerization by heat, and an initiator that decomposes at 150 to 250°C is preferable.

As the polymerization initiator, a compound having at least an aromatic group is preferred, and examples thereof include an acylphosphine compound, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, and a benzoin ether compound. Thioxanthone compounds, oxime compounds, hexaarylbisimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazo compounds, iodonium compounds, arsenic compounds, azinium compounds, benzoin ethers Compounds, ketal derivative compounds, onium salt compounds, organic boron salt compounds, and dioxin compounds. From the viewpoint of sensitivity, the oxime compound, hydroxyacetophenone compound, aminoacetophenone compound, acetylphosphine compound, α-aminoketone compound, trihalomethyl compound, hexaarylbisimidazole compound or thiol Compounds are preferred, and oxime compounds are more preferred. Examples of hydroxyacetophenone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF). Examples of the aminoacetophenone compounds include IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF). Examples of the acetylphosphine compound include IRGACURE-819 and DAROCUR-TPO (trade names: all manufactured by BASF Corporation). Examples of the oxime compound include IRGACURE OXE 01 (1,2-octanedione, 1-[4-(phenylthio)-, 2-(o-benzoyl oxime)]) and IRGACURE OXE 02 (ethanone , 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(o-acetoxime)), IRGACUREOXE03 (trade name: BASF company Manufacturing), IRGACUREOXE04 (trade name: manufactured by BASF). As the oxime compound, the following formulas (OX-1), (OX-2) or (OX-2) of paragraph 0513 (corresponding to <0632> of US Patent Application Publication No. 2012/235099) can be referred to The description of the compound represented by (OX-3), and such contents are incorporated in the specification of this application.

Examples of the oxime compound include the polymerization initiators described in paragraphs 0092 to 0096 of Japanese Patent Laid-Open No. 2012-113104, and the contents thereof are incorporated in the specification of the present application. In addition, as commercial products of oxime compounds, TRONLY TR-PBG-304, TRONLY TR-PBG-309, and TRONLY TR-PBG-305 (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD) manufacturing).

The content of the polymerization initiator in the photosensitive composition is not particularly limited, but from the viewpoint of excellent drying resistance, it is preferably 0.1 to 10% by mass relative to the total mass of the photosensitive composition, and 0.5 to 5.0 mass % Is better. One type of polymerization initiator may be used alone, or two or more types may be used in combination.

(Polymerization inhibitor) As a polymerization inhibitor, a well-known polymerization inhibitor can be mentioned. It is speculated that the polymerization inhibitor has a function of capturing free radicals generated when the color filter disposed adjacent to the hardened layer is heated. For example, phenol compounds, hindered amine compounds, phosphorus compounds, and phenothiazine compounds may be mentioned. Among them, a hindered phenol compound, a phenol compound other than the hindered phenol compound, a benzoquinone compound, or a hydroquinone compound is preferable from the viewpoint that the effect of the present invention is more excellent. In addition, the hindered phenol compound is a phenol compound having a substituent other than a hydrogen atom in at least one of two ortho positions of the phenolic hydroxyl group. Examples of the substituent include an alkyl group (preferably an alkyl group other than methyl), alkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, amine group, and substituted amine group , Alkylthio, phenylthio and halogen atoms.

As the hindered phenol compound, the compound represented by formula (X) is preferred.

[Chemical Formula 1]

In formula (X), R ¹ and R ² each independently represent a substituent. The definition of the substituent is as described above, among which alkyl, alkenyl, alkynyl or aryl is preferred, and alkyl having 4 or more carbon atoms is more preferred. R ³ represents a substituent. The definition of the substituent is as described above, wherein alkyl, alkenyl, alkynyl or aryl is preferred, and alkyl is preferred. When n is 2 or more, a plurality of R ³ may be the same or different. n represents an integer of 0 to 3. Among them, 1 is better.

As the phenol compound other than the hindered phenol compound, the compound represented by the formula (Y) is preferable.

[Chemical Formula 2]

In formula (Y), R ⁴ represents a substituent. The definition of the substituent is as described above, wherein alkyl, alkenyl, alkynyl, aryl or alkoxy is preferred, and alkoxy is more preferred. m represents an integer of 0 to 3. Among them, 1 is better.

As the benzoquinone compound, the compound represented by formula (Z) is preferred.

[Chemical Formula 3]

In formula (Z), R ⁵ to R ⁸ each independently represent a hydrogen atom or a substituent. The definition of the substituent is as described above, and aryl, amine, substituted amine or halogen atom is preferred. Examples of benzoquinone compounds include o-benzoquinone and p-benzoquinone.

As the hydroquinone compound, the compound represented by formula (V) is preferred.

[Chemical Formula 4]

In formula (V), R ⁹ represents a substituent. The definition of the substituent is as described above, wherein alkyl, alkenyl, alkynyl, aryl or alkoxy is preferred, and alkyl is more preferred. When p is 2 or more, a plurality of R ⁹ may be the same or different. p represents an integer of 0-4. Among them, 1 is better.

One type of polymerization inhibitor may be used alone, or two or more types may be used in combination. Among them, from the viewpoint that the effect of the present invention is more excellent, it is preferable that the photosensitive composition contains two or more kinds of polymerization inhibitors. In addition, when the photosensitive composition contains two or more kinds of polymerization inhibitors, the polymerization inhibitor is selected from the group consisting of hindered phenol compounds, hindered phenol compounds, phenol compounds, benzoquinone compounds, and hydroquinone compounds. At least two or more of the groups are preferred. In addition, from the viewpoint that the effect of the present invention is more excellent, the polymerization inhibitor includes one or more first polymerization inhibitors and hindered phenols selected from the group consisting of hindered phenol compounds, benzoquinone compounds, and hydroquinone compounds. Phenolic compounds other than compounds are preferred. In addition, the mass ratio of the content of the phenol compound other than the hindered phenol compound to the total content of the first polymerization inhibitor is not particularly limited, but from the viewpoint that the effect of the present invention is more excellent, 0.0009 to 0.17 is preferable .

The content of the polymerization inhibitor in the photosensitive composition is not particularly limited, but from the viewpoint that the effect of the present invention is more excellent, it is preferably 0.0001 to 0.30% by mass relative to the total mass of the photosensitive composition, and 0.002 to 0.20 Quality% is better.

(UV absorber) The ultraviolet absorber refers to one that does not have the function of initiating the polymerization of the polymerizable compound by light or heat (that is, it does not meet the polymerization initiator). Here, "does not have the function of initiating the polymerization of the polymerizable compound" means that even if the ultraviolet absorber actually receives light or heat energy, no active species for initiating the polymerization of the polymerizable compound will be generated.

It is preferable that the ultraviolet absorber system not only does not have the function of initiating the polymerization of the polymerizable compound, but also does not have the characteristics of the sensitizer described below. Here, the characteristics of the sensitizer refer to the characteristics of initiating polymerization by transferring the energy obtained by absorbing light itself to other substances (polymerization initiator, etc.).

The ultraviolet absorber preferably has a maximum absorption wavelength in the range of 300-430 nm, and more preferably has a maximum absorption wavelength in the range of 330-420 nm. It is further preferable that the ultraviolet absorber has a maximum absorption wavelength in at least one of (I) wavelength range of 340 to 380 nm, (II) wavelength range of 380 to 420 nm, and (III) wavelength range of 420 to 450 nm.

When the thermal mass of the ultraviolet absorber is measured, the mass reduction rate at 150°C is preferably 5% or less, and more preferably 3% or less. The lower limit is not particularly limited, and 0% can be cited. If the mass reduction rate at 150° C. is within the above range, the ultraviolet absorber hardly decomposes during exposure to be described later, and it easily functions as an ultraviolet absorber. In addition, when the thermal mass of the ultraviolet absorber is measured, the mass reduction rate at 220° C. is preferably 40% or more, more than 40% is more preferable, and 70% or more is still more preferable. The upper limit is not particularly limited, and 100% can be cited. If the mass reduction rate at 220°C is within the above range, the ultraviolet absorber will decompose during the heat treatment performed after exposure, and coloration from the ultraviolet absorber can be suppressed. The conditions for measuring the thermal mass of the ultraviolet absorber are as follows. That is, under a nitrogen atmosphere, the ultraviolet absorber was heated from a state of 25°C to 100°C at a temperature increase rate of 10°C/min. After maintaining at 100°C for 30 minutes, the ultraviolet absorber was heated to 220°C at a temperature increase rate of 10°C/min and held at 220°C for 30 minutes. When the ultraviolet absorber is held at 100°C for 30 minutes, the average value of the mass of the ultraviolet absorber from 24 to 29 minutes after the start of the retention is taken as the reference value (100%) of the mass of the ultraviolet absorber, measured at 150°C And the mass of the ultraviolet absorber after heating at 220°C for 30 minutes, the mass reduction rate was calculated according to the following formula. Mass reduction rate (%) at 150°C=100-(Quality value of the mass of UV absorber at 150°C/mass of UV absorber)×100 Mass reduction rate (%) at 220°C=100-(mass value of ultraviolet absorber after heating at 220°C for 30 minutes/reference value of mass of ultraviolet absorber)×100

The type of ultraviolet absorber is not particularly limited, and examples thereof include dibenzoylmethane-based compounds, aminobutadiene-based compounds, salicylate-based compounds, benzophenone-based compounds, and benzotriazole-based compounds. Among the compounds, substituted acrylonitrile-based compounds and triazine-based compounds, dibenzoylmethane-based compounds or aminobutadiene-based compounds are preferred. Examples of the dibenzoylmethane-based compound (dibenzoylmethane-based ultraviolet absorber) include 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, and 4-isopropyldibenzene Methane, 4-tert-butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'-diisopropyl Dibenzoylmethane, 4,4'-dimethoxydibenzoylmethane, 4-third butyl-4'-methoxydibenzoylmethane (avobenzone), 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane, 2-methyl-5-third butyl-4'-methoxydibenzoylmethane and 2,4 -Dimethyl-4'-methoxydibenzoylmethane, 2,6-dimethyl-4-third butyl-4'-methoxydibenzoylmethane. Examples of the aminobutadiene-based compound (aminobutadiene-based ultraviolet absorber) include compounds having a partial structure represented by formula (1). In formula (1), * represents the bonding position.

[Chemical Formula 5]

Examples of the salicylate-based compound (salicylate-based ultraviolet absorber) include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of the benzophenone-based compound (benzophenone-based ultraviolet absorber) include 2,2'-dihydroxy-4-methoxybenzophenone and 2,2'-dihydroxy-4,4 '-Dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone Methone and 2-hydroxy-4-octyloxybenzophenone. As the benzotriazole-based compound (benzotriazole-based ultraviolet absorber), 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzo Triazole, 2-(2'-hydroxy-3'-third butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-third pentan Group-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole Azole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di- Third butylphenyl) benzotriazole, 2-(2'-hydroxy-5'-methylphenyl) benzotriazole and 2-[2'-hydroxy-5'-(1,1,3 ,3-tetramethyl)phenyl]benzotriazole. Examples of the substituted acrylonitrile-based compound (substituted acrylonitrile-based ultraviolet absorber) include 2-cyano-3,3-diphenyl acrylate and 2-cyano-3,3-diphenyl 2-ethylhexyl acrylate. Examples of the triazine-based compound (triazine-based ultraviolet absorber) include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4 ,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]- 2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6- Bis(2,4-dimethylphenyl)-1,3,5-triazine and other mono(hydroxyphenyl)triazine compounds; 2,4-bis(2-hydroxy-4-propoxyphenyl) -6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6- (4-methylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-di Bis(hydroxyphenyl)triazine compounds such as methylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4 -Dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2, 4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine and other tris(hydroxyphenyl)triazine compounds. In addition to the above, a diethylamino-phenylsulfonyl-pentadienoate ultraviolet absorber (manufactured by FUJIFILM Finechemicals Co., Ltd., trade name: DPO) can also be mentioned. Also, refer to the compound represented by any one of the general formulas (1) to (8) or the following paragraphs 0103 of Japanese Patent Application Laid-Open No. 2012-032556 (corresponding to page 30 of WO2012/015076) Specific examples (1-1) to (8-3), these contents are incorporated in the specification of this application.

The content of the ultraviolet absorber in the photosensitive composition is not particularly limited, but relative to the total mass of the photosensitive composition, 0.01 to 10.0 mass% is preferable, and 0.05 to 1.50 mass% is more preferable. One type of ultraviolet absorber may be used alone, or two or more types may be used in combination.

In the photosensitive composition, the mass ratio of the content of the ultraviolet absorber to the content of the polymerization inhibitor is 0.08 to 330. From the viewpoint that the effect of the present invention is more excellent, 0.1 to 200 is preferable, and 3 to 30 is more good. In addition, from the viewpoint of excellent rectangularity, 20 or more is more preferable.

The photosensitive composition may contain components other than the above-mentioned components, and examples thereof include resin binders, sensitizers, solvents, surfactants, dispersants, crosslinking agents, and hardening accelerators. Hereinafter, each component will be described in detail.

(Resin adhesive) Examples of the resin binder include (meth)acrylic resins, urethane resins, polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, polyamide, polyester, and poly Acetylene imide and polybenzoxazole, (meth)acrylic resin or urethane resin are preferred. In addition, as a resin binder, an alkali-soluble binder (alkali-soluble resin) is also preferable. When the photosensitive composition contains an alkali-soluble binder, when the coating film obtained from the photosensitive composition is exposed, the unexposed portion can be easily removed with an alkali developer. Examples of the alkali-soluble adhesives include (meth)acrylic resins, urethane resins, polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, polyvinyl amide, polyester, Polyimide or its precursor and polybenzoxazole or its precursor are preferably (meth)acrylic resins or urethane resins. As polyimide or its precursor and polybenzoxazole or its precursor, see the description of paragraphs 0012 to 0046 of WO2011/067998 and paragraphs 0020 to 0054 of Japanese Patent Laid-Open No. 2013-050593 The description of the described polyimide resin, and such contents are incorporated in the specification of this application.

It is preferable that the alkali-soluble adhesive has an acid group. Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, and a sulfonamide group. From the viewpoint of obtaining a raw material, a carboxylic acid group is preferred. As the alkali-soluble binder having an acid group, a polymer obtained by using a polymerizable compound having an acid group is preferable. From the viewpoint of adjusting the acid value, by combining the polymerizable compound having an acid group and a non-acid The copolymer obtained by copolymerizing the base polymerizable compound is more preferable. Examples of the polymerizable compound having an acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and p-carboxystyrene, acrylic acid, methacrylic acid or p-carboxybenzene Ethylene is preferred.

Examples of the polymerizable compound having no acid group include (meth)acrylates (alkyl esters, aryl esters, and aralkyl esters). The alkyl group in the alkyl ester portion of the (meth)acrylate may be linear or branched. The alkyl group having 1 to 10 carbon atoms is preferred, and the alkyl group having 1 to 6 carbon atoms is more preferred. good. As the aryl group in the aryl ester portion of the (meth)acrylate, aryl groups having 6 to 14 carbon atoms are preferred, and aryl groups having 6 to 10 carbon atoms are more preferred. As the aralkyl group in the aralkyl ester portion of the (meth)acrylate, an aralkyl group having 7 to 20 carbon atoms is preferred, and an aralkyl group having 7 to 12 carbon atoms is more preferred.

The content of acid groups in the alkali-soluble adhesive is not particularly limited, but from the viewpoint of alkali developability and the strength of the resulting cured film, 0.5 to 4.0 meq/g is preferred, and 0.5 to 3.0 meq/g is Better.

It is preferable that the alkali-soluble adhesive further has a crosslinkable group. In this way, in particular, both the curability of the exposed portion and the alkali developability of the unexposed portion can be improved, and a pattern with high durability can be obtained. The crosslinkable group refers to a group that crosslinks the resin binder during the polymerization reaction that occurs in the coating film when the coating film obtained from the photosensitive composition is exposed or heated. Examples of the crosslinkable group include a polymerizable group (for example, an ethylenically unsaturated bonding group as a functional group capable of addition polymerization reaction), an amine group, and an epoxy group. Among them, the double bond group is preferable, and the ethylenically unsaturated double bond group is more preferable. In addition, the crosslinkable group may be a functional group capable of becoming a radical by light irradiation, and examples thereof include a thiol group and a halogen group. Among them, as the crosslinkable group, an ethylenically unsaturated double bond group is preferred. As the ethylenically unsaturated double bond group, styryl, (meth)acryloyl or allyl is preferred, and (meth)acryloyl is more preferred.

The content of the crosslinkable group in the alkali-soluble adhesive is not particularly limited, but 0.5 to 3.0 meq/g is preferred, 1.0 to 3.0 meq/g is more preferred, and 1.5 to 2.8 meq/g is particularly preferred. Here, the content (meq/g) can be measured by, for example, iodine value titration. The alkali-soluble adhesive having a crosslinkable group is described in detail in Japanese Patent Application Publication No. 2003-262958, and the compounds described therein can also be used in the present invention.

As one of the preferable forms of the alkali-soluble binder, a single-volume component containing a compound represented by the following general formula (ED) (hereinafter, also referred to as "ether dimer") can be exemplified The resulting polymer (hereinafter, also referred to as "specific polymer."). If a specific polymer is used, the infrared light cut filter has more excellent pattern formability.

[Chemical Formula 6]

In the general formula (ED), R ₁ and R ₂ each represent a hydrogen atom or a C 1-25 hydrocarbon group which may have a substituent. Examples of the hydrocarbon groups having 1 to 25 carbon atoms which may have substituents represented by R ₁ and R ₂ include linear or branched alkyl groups; aryl groups; alicyclic groups; and alkoxy-substituted Alkyl; alkyl substituted by aryl such as benzyl; etc. Among them, a methyl group, an ethyl group, a cyclohexyl group, or a benzyl group is preferred from the viewpoint of excellent heat resistance of the substituent.

As specific examples of the ether dimer, specific examples of the ether dimer described in paragraph 0565 of Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to paragraph 0694 of US Patent Application Publication No. 2012/235099) For example, such content is incorporated into the specification of this application. Among them, dimethyl-2,2'-[oxybis(methylene)]bis-2-propionate, diethyl-2,2'-[oxybis(methylene)]bis- 2-propionate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-propionate or dibenzyl-2,2'-[oxybis(methylene )] Bis-2-propionate is preferred. These ether dimers may be only one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) can copolymerize other monomers.

The content of the repeating unit derived from the ether dimer in a specific polymer is preferably 1 to 50 mol%, and more preferably 1 to 20 mol% relative to all the repeating units in the alkali-soluble binder. It is also possible to copolymerize other monomers together with the ether dimer. Examples of other single bodies include a single body for introducing an acid group, a single body for introducing a radically polymerizable double bond, a single body for introducing an epoxy group, and others other than these Monomer capable of copolymerization. Only one type may be used for these single masses, or two or more types may be used.

Examples of the single unit for introducing an acid group include monomers having a carboxyl group such as (meth)acrylic acid and itaconic acid, and monomers having a phenolic hydroxyl group such as N-hydroxyphenyl maleimide. Monomers such as maleic anhydride and itaconic anhydride. Among them, (meth)acrylic acid is preferred. In addition, the single body for introducing an acid group may be a single body capable of imparting an acid group after polymerization, for example, a single body having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, (methyl ) Monomers with epoxy groups such as glycidyl acrylate and isocyanate groups such as 2-isocyanate (meth)ethyl acrylate. When a single unit capable of imparting an acid group after polymerization is used, it is necessary to perform a treatment for imparting an acid group after polymerization. As a treatment for giving an acid group after polymerization, for example, in the case of using a single body having a hydroxyl group, a treatment for adding an acid anhydride of succinic anhydride, tetrahydrophthalic anhydride, and maleic anhydride may be mentioned. .

When the single body component containing the compound represented by the general formula (ED) contains a single body for introducing acid groups, the content of the single body for introducing acid groups is 5 to 5 relative to the total mass of the single body components 70% by mass is better, and 10-60% by mass is more preferable.

Examples of the monomers for introducing radical polymerizable double bonds include monomers having a carboxyl group such as (meth)acrylic acid and itaconic acid; those having a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride Monomer; glycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate and o-(or m-or p-) vinylbenzyl glycidyl ether etc. have epoxy groups Of monomers. When using a single volume for introducing radically polymerizable double bonds, it is necessary to perform a treatment for imparting radically polymerizable double bonds after polymerization. As a treatment for imparting radical polymerizable double bonds after polymerization, for example, when a monomer having a carboxyl group is used, glycidyl (meth)acrylate, 3,4 (meth)acrylic acid -Addition treatment of epoxy cyclohexyl methyl ester and o-(or m- or p-) vinylbenzyl glycidyl ether and other compounds with epoxy group and free radical polymerizable double bond.

When the single body component containing the compound represented by the general formula (ED) contains a single body for introducing radical polymerizable double bonds, the content of the single body for introducing radical polymerizable double bonds is The total mass of the body composition is preferably 5 to 70% by mass, and more preferably 10 to 60% by mass.

Examples of the single-quantity body for introducing epoxy groups include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, and o-(or m-or p- ) Vinyl benzyl glycidyl ether. When the single body component containing the compound represented by the general formula (ED) contains the single body for introducing the epoxy group, the content of the single body for introducing the epoxy group relative to the total mass of the single body component, It is preferably 5 to 70% by mass, and more preferably 10 to 60% by mass.

When a polymer obtained by polymerizing a single component containing a compound represented by the general formula (ED) contains other single components capable of copolymerization, the content ratio is not particularly limited, but 95% by mass or less is Good, 85% by mass or less is even better.

The weight-average molecular weight of the specific polymer is not particularly limited, but from the viewpoint of the heat resistance of the coating film formed of the photosensitive composition, 2,000 to 200,000 are preferred, 5,000 to 100,000 are more preferred, and 5,000 to 20,000 are Further preferred. In addition, when the specific polymer has an acid group, the acid value is preferably 30 to 500 mgKOH/g, and more preferably 50 to 400 mgKOH/g.

As a polymerization method suitable for the synthesis of a specific polymer, various conventionally known polymerization methods can be used, and a solution polymerization method is preferred. In detail, for example, in accordance with the method of synthesizing the polymer (a) described in Japanese Patent Laid-Open No. 2004-300204, it is possible to synthesize a polymer obtained by polymerizing a single component containing a compound represented by the general formula (ED) Thing.

Hereinafter, exemplary compounds of specific polymers are shown, but the present invention is not limited to these. The composition ratio of the exemplified compounds shown below is mole %. Examples of commercially available products include Acrycure RD-F8 (acrylic resin) (manufactured by NIPPON SHOKUBAI CO., LTD.) and the like.

[Chemical Formula 7]

[Chemical Formula 8]

The content of the resin binder (especially alkali-soluble binder) in the photosensitive composition is not particularly limited, but from the viewpoint that the strength of the infrared light cut filter is more excellent and the photolithography and residue are improved, relative to The total mass of the photosensitive composition is preferably 5-50% by mass, and more preferably 10-25% by mass.

(Solvent) The type of solvent is not particularly limited, and water and organic solvents can be mentioned. Examples of the solvent include solvent A having a boiling point of 170 to 200°C at 1 atmosphere. The boiling point of the solvent A is 170 to 200°C, preferably 180 to 193°C.

As one of the preferable aspects of the solvent A, in the solvent A, it is preferable to include 3 or more oxygen atoms in the molecule, the number of oxygen atoms is preferably 3 to 5, and 3 is still more preferable. As a preferable aspect of the solvent A, a solvent represented by the following formula (X) or formula (Y) may be mentioned. Formula (X) R ¹ O-(LO) _n -R ² Formula (Y) R ¹ O-(LO) _m -CO-R ^{2 In} formula (X) and formula (Y), R ¹ represents a hydrogen atom or an alkane base. The number of carbons contained in the alkyl group is not particularly limited, but 1 to 3 is preferred, and 1 is more preferred. R ² represents an alkyl group. The number of carbons included in the alkyl group is preferably 1 to 3, and 1 is more preferable. L represents alkylene. The number of carbons contained in the alkylene group is preferably 3 to 5, and 3 is more preferable. n represents an integer of 2 to 4. m represents an integer of 1-2. Specific examples of the solvent A include dipropylene glycol monomethyl ether (boiling point 188°C), cyclohexanol acetate (boiling point 173°C), dipropylene glycol dimethyl ether (boiling point 171°C), ethylene glycol monobutyl ether Acetate (boiling point 192°C), diethylene glycol diethyl ether (boiling point 189°C), diethylene glycol monomethyl ether (boiling point 194°C), propylene glycol diacetate (boiling point 190°C), 3-methoxy Butyl acetate (boiling point 171℃), propylene glycol n-butyl ether (boiling point 170℃), diethylene glycol ethyl methyl ether (boiling point 176℃) and diethylene glycol isopropyl methyl ether (boiling point 179℃). In addition, as one of the preferable aspects of the solvent A, it is preferable that the solvent A contains the solvent represented by the above formula (X) or formula (Y) as a main component. The main component means that the content of the solvent represented by formula (X) or formula (Y) exceeds 50% by mass relative to the total mass of the solvent A. In addition, as one of other preferable aspects of the solvent A, it is preferable that the solvent A include a solvent (for example, dipropylene glycol monomethyl ether) mentioned as a specific example of the solvent A as the main component. The main component means that the content of the solvent mentioned as a specific example of the solvent A exceeds 50% by mass relative to the total mass of the solvent A.

The content of the solvent A in the photosensitive composition relative to the total mass of the photosensitive composition is preferably 0.1 to 20% by mass, and more preferably 0.3 to 5.0% by mass.

The photosensitive composition includes a solvent B1 selected from the group consisting of a solvent B1 having a boiling point of 100 to 130°C at 1 atmosphere and a solvent B2 having a boiling point of more than 130°C and less than 170°C at 1 atmosphere. good. The boiling point of the solvent B1 at 1 atm is 100 to 130°C, preferably 120 to 130°C. The boiling point of the solvent B2 at 1 atmosphere pressure exceeds 130°C and less than 170°C, preferably 140 to 150°C.

Examples of the solvent B1 include butyl acetate (boiling point 126°C), ethylene glycol monomethyl ether (boiling point 125°C), methyl n-butyl ketone (boiling point 127°C), and tetrahydrofuran (boiling point 126°C). Examples of the solvent B2 include propylene glycol 1-monomethyl ether 2-acetate (boiling point 145°C), ethylene glycol monomethyl ether acetate (boiling point 145°C), ethyl lactate (boiling point 155°C), diethyl ether Glycol dimethyl ether (boiling point 162°C), 3-methoxybutanol (boiling point 161°C) and propylene glycol n-propyl ether (boiling point 150°C).

The content of the solvent B in the photosensitive composition relative to the total mass of the photosensitive composition is preferably 20 to 90% by mass, and more preferably 40 to 70% by mass. The mass ratio of solvent A to solvent B in the photosensitive composition (mass of solvent A/mass of solvent B) is preferably 0.005 to 0.500, and more preferably 0.010 to 0.200. When the solvent B1 is included in the photosensitive composition, the content of the solvent B1 in the photosensitive composition is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5.0% by mass relative to the total mass of the photosensitive composition. When the solvent B2 is included in the photosensitive composition, the content of the solvent B1 in the photosensitive composition is preferably 20 to 80% by mass and more preferably 30 to 70% by mass relative to the total mass of the photosensitive composition. Solvent B may use only 1 type, and may use 2 or more types together. Among them, from the viewpoint that the effect of the present invention is more excellent, it is preferable to use the solvent B1 and the solvent B2 together. When the solvent B1 and the solvent B2 are used together, the mass ratio of the solvent B1 and the solvent B2 (the mass of the solvent B1/the mass of the solvent B2) is preferably 0.005 to 0.500, and more preferably 0.010 to 0.200.

(Surfactant) From the viewpoint of further improving coatability, a surfactant may be included in the photosensitive composition. In addition, when the surfactant is contained in the photosensitive composition, the pattern rectangularity is more excellent. Examples of the surfactant include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicone-based surfactants, fluorine-based surfactants or silicone-based interfaces Active agents are preferred.

Examples of fluorine-based surfactants include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F475, Megafac F482, Megafac F554, Megafac F780, Megafac F781, Megafac F781F (made by DIC CORPORATION above), Fluorad FC430, Fluorad FC431, Fluorad FC171 (made by Sumitomo 3M Limited above), Surflon S-382, Surflon SC-101, Surflon SC -103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (above manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. In addition, the surfactants described in paragraph 0552 of Japanese Patent Laid-Open No. 2012-208494 (corresponding to <0678> in the specification of US Patent Application Publication No. 2012/0235099) and the like can be cited. In the application manual. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene sorbitan fats. Acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene-oxypropylene block copolymer, acetylene glycol-based surfactant, and acetylene-based polyoxyethylene oxide. Examples of the cationic surfactants include the cationic surfactants described in paragraph 0554 of Japanese Patent Laid-Open No. 2012-208494 (corresponding to <0680> of US Patent Application Publication No. 2012/0235099), which The contents of etc. are incorporated into the specification of this application. Examples of the anionic surfactants include W004, W005, and W017 (manufactured by Yusho Co., Ltd.). Examples of silicone-based surfactants include those described in paragraph 0556 of Japanese Patent Laid-Open No. 2012-208494 (corresponding to <0682> of US Patent Application Publication No. 2012/0235099) and the like. Agents, and such contents are incorporated into the specification of this application.

From the viewpoint that the intensity of the infrared cut filter is more excellent, the content of the surfactant in the photosensitive composition is preferably 0.0001 to 0.1000% by mass relative to the total mass of the photosensitive composition, and more preferably 0.0010 to 0.0700% by mass. good.

(Dispersant) A dispersant may be included in the photosensitive composition. By including a dispersant, the dispersion stability of specific particles in the photosensitive composition is improved. In addition, the dispersant also functions as the above-mentioned binder. Examples of the dispersant include polymer dispersants [for example, polyamidoamine and its salts, polycarboxylic acid and its salts, high molecular weight unsaturated acid esters, modified polyurethane esters, modified polyesters, and modified poly(A Base) acrylate, (meth)acrylic copolymer and formalin condensate of naphthalene sulfonate], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine and alkanolamine. Examples of the polymer dispersant include linear polymers, terminal modified polymers, graft polymers, and block polymers.

Examples of the terminal-modified polymer include polymers having a phosphate group at the terminal, polymers having a sulfonic acid group at the terminal, polymers having a partial skeleton of organic dyes or heterocycles, and polymers having hydroxyl groups at one terminal. Or an amine-based oligomer or polymer modified with an acid anhydride to produce a polymer. Examples of the graft-type polymer include a reaction product of poly(lower alkyleneimine) and polyester, a reaction product of polyallylamine and polyester, an amphoteric dispersion resin having a basic group and an acid group, and having Copolymers of grafted polymers and macromonomers with partial skeletons or heterocycles of organic pigments and monomers containing acid groups. As the macromonomer used in the production of the graft-type polymer by radical polymerization, a known macromonomer can be mentioned, and the macromonomer AA-6 (terminal group is manufactured by TOAGOSEI CO., LTD. Methacryloyl-based polymethyl methacrylate), AS-6 (polystyrene with methacryloyl end groups), AN-6S (styrene and acrylonitrile with methacryloyl end groups) Copolymer), AB-6 (polybutyl acrylate with a terminal methacryloyl group), PLACCEL FM5 (ε-caprolactone 2-hydroxyethyl methacrylate 5) manufactured by Daicel Chemical Industries, Ltd. Molar equivalent plus product), FA10L (2-hydroxyethyl acrylate ε-caprolactone 10 mole equivalent plus product), and polyester-based macromonomers described in Japanese Patent Laid-Open No. 2-272009. Among them, polyester-based macromonomers are preferred from the viewpoint of excellent flexibility and solvent affinity. As the block-type polymer, the block-type polymers described in JP 2003-049110, JP 2009-052010, etc. are preferred.

Examples of the dispersant include "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylate), 110 (copolymer containing acid group), 130 (polyamide), 161 manufactured by BYK Chemie. , 162, 163, 164, 165, 166, 170 (polymer copolymer)", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", "EFKA4047, 4050, 4010 (polyurethane series ), EFKA4330, 4340 (block copolymer), 4400～4402 (modified polyacrylate), 5010 (polyesteramide), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative)”, Ajinomoto Fine- "AJISPER PB821, PB822, PB880, PB881" manufactured by Techno Co., Inc., "Florene TG-710 (urethane oligomer)" manufactured by KYOEISHA CHEMICAL Co., LTD., "Plyfolw No. 50E , No. 300 (acrylic copolymer), "DISPARLON KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703 manufactured by Kusumoto Chemicals, Ltd. -50, DA-705, DA-725", "DEMOL RN, N (formalin polycondensate of naphthalenesulfonic acid), MS, C, SN-B (formalin polycondensate of aromatic sulfonic acid)" manufactured by Kao Corporation, "HOMOGENOL L-18 (polymeric polycarboxylic acid)", "Emalgen920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "Acetamine 86 (stearylamine acetate)", Lubrizol Japan Ltd .Manufactured "SOLSPERSE 5000 (phthalocyanine derivatives), 13240 (polyesteramine), 3000, 17000, 27000 (polymer with functional part at the end), 24000, 28000, 32000, 38500 (grafted polymer )”, “NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)” manufactured by Nikko Chemicals Co., Ltd., Kawaken Fine Chemicals Co., Ltd.'s HINOACT T-8000E, etc., Shin-Etsu Chemical Co., Ltd.'s organosiloxane polymer KP-341, Yusho Co., Ltd.'s "W001: cationic surfactant", polymer oxygen Ethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol Nonionic surfactants such as alcohol distearate, sorbitan fatty acid esters, anionic surfactants such as "W004, W005, W017", "EFKA-46, EFKA-" manufactured by MORISHITA & CO., LTD. 47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450", "DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100" manufactured by SAN NOPCO LIMITED, etc. Polymer dispersant, "ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123" manufactured by ADEKA CORPORATION And "IONET (trade name) S-20" manufactured by SANYO KASEI CO., LTD., etc.

When a dispersant is used, first, after preparing a dispersion composition from specific particles (and other infrared light shielding agents as needed) and a dispersant and an appropriate solvent, it is blended into the composition from the viewpoint of improving dispersibility Words are better. The content of the dispersant in the photosensitive composition is preferably 10 to 70% by mass, and more preferably 30 to 60% by mass relative to the total mass of specific particles.

(Sensitizer) A sensitizer may be included in the photosensitive composition. When the sensitizer is included in the photosensitive composition, the pattern rectangularity is more excellent. As the sensitizer, it is preferable to sensitize the photopolymerization initiator by an electron moving mechanism or an energy moving mechanism. The type of sensitizer used is not particularly limited, and examples thereof include compounds exemplified in paragraph 0202 of Japanese Patent Laid-Open No. 2012-122045. The content of the sensitizer in the photosensitive composition relative to the total solid content in the photosensitive composition is preferably 0.01 to 10.0% by mass, and more preferably 0.10 to 4.0% by mass.

(Crosslinking agent) A crosslinking agent may be included in the photosensitive composition. By including a cross-linking agent in the photosensitive composition, it is expected to increase the strength of the infrared light cut filter. The crosslinking agent is preferably a compound having two or more crosslinkable groups. Examples of the crosslinkable group include an oxetanyl group, a cyanate group, and the same groups as those mentioned for the crosslinkable group that the alkali-soluble binder can have, and epoxy groups and oxetane groups Butyl groups or cyanate groups are preferred. That is, as the crosslinking agent, epoxy compounds, oxetane compounds or cyanate compounds are preferred. The type of crosslinking agent used is not particularly limited, and examples thereof include compounds exemplified in paragraphs 0204 to 0209 of Japanese Patent Application Laid-Open No. 2012-122045.

(Hardening accelerator) A hardening accelerator may be included in the photosensitive composition. The type of hardening accelerator used is not particularly limited, and examples thereof include compounds exemplified in paragraph 0211 of Japanese Patent Laid-Open No. 2012-122045.

The photosensitive composition can be prepared by mixing the above components. The use of the photosensitive composition is not particularly limited, but it is preferably used for forming an infrared light shielding layer, and more preferably used for forming an infrared light cut filter. That is, the cured film formed using the photosensitive composition is preferably used for the infrared light shielding layer. The infrared cut filter formed using the photosensitive composition of the present invention can also be used for, for example, an infrared cut filter on the light-receiving side of a solid-state imaging element and the back side (the side opposite to the light-receiving side) of the solid-state imaging element Infrared light cut filter. In addition, the photosensitive composition of the present invention may be directly applied to a color filter or a planarization layer and used for forming a coating film. Since the photosensitive composition of the present invention can be supplied in a state where it can be applied, the infrared light cut filter can be easily formed in a desired member or position of the solid-state imaging element.

<Infrared cut filter> Next, the infrared cut filter of the present invention will be described. The infrared cut filter of the present invention is formed using the above-mentioned photosensitive composition of the present invention. The film thickness of the infrared light cut filter can be appropriately selected according to the purpose, preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. In order to maintain the light-shielding ability, the lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more. The maximum transmittance of the infrared light cut filter at a wavelength of 400 to 1300 nm is not particularly limited, but it is preferably 60% or more, and more preferably 65% or more. In addition, the maximum transmittance of the infrared light cut filter at a wavelength of 900 to 1300 nm is not particularly limited, but it is preferably 20% or less, more preferably 10% or less, and most preferably 5% or less.

Infrared cut-off filters are used for lenses that have the function of absorbing or cutting off infrared light (lenses for cameras such as digital cameras, mobile phones, and car cameras, and optical lenses such as f-θ lenses and pick-up lenses), and semiconductor light reception Optical filters for components, infrared cut-off filters for proximity illuminance sensors, infrared cut-off filters or infrared absorbers for energy-saving hot-line blocking, agricultural coatings for the purpose of selective utilization of sunlight, use Infrared light absorption heat recording media, near-infrared cutoff filters for electronic devices or photographs, protective glasses, sunglasses, hot-line blocking films, optical text reading records, confidential document copying prevention, electronic photoreceptors and Laser welding, etc. In particular, it is useful for noise-cut filters for CCD (Charge Coupled Device) cameras or filters for CMOS (Complementary Metal Oxide Semiconductor) image sensors.

The method of manufacturing the infrared light cut filter is not particularly limited, and can be manufactured through a process of forming a coating film by applying the photosensitive composition of the present invention to a support. In addition, as will be described later, a patterning process may be further performed.

As a method of forming the coating film, for example, the above-mentioned photosensitive film can be exemplified by a drop method (drop casting), a spin coating method, a slit spin coating method, a slit coating method, a screen printing method, and an applicator coating method. A method of applying a sexual composition to a support. The support to which the photosensitive composition of the present invention is applied may be a transparent substrate containing glass or the like. Moreover, it may be each base material in a solid-state imaging element. In addition, it may be another substrate provided on the light-receiving side of the solid-state imaging element. In addition, it may be a layer such as a planarization layer provided on the light-receiving side of the solid-state imaging element.

As a method of manufacturing a pattern-shaped infrared light cut filter, for example, a process including applying the photosensitive composition of the present invention on a support to form a coating film, a process of exposing the coating film in a pattern, and A method of developing a patterning process that removes unexposed parts. In addition, exposure is used to mean not only light of various wavelengths but also radiation irradiation such as electron beams and X-rays. The exposure is preferably performed by irradiation of radiation. Examples of radiation include ultraviolet light, visible light, and electron beams, and more specifically, KrF, ArF, g-rays, h-rays, and i-rays. Examples of the exposure method include stepper exposure and exposure based on a high-pressure mercury lamp. The exposure amount is preferably 5 to 3000 mJ/cm ^{2, and more} preferably 10 to 2000 mJ/cm ² .

In the above, the method of forming the pattern by the development process has been described, but the dry etching method may also be used to form the pattern. In the manufacturing method of the infrared cut filter, other processes may be included. Examples of other processes include a surface treatment process of a support, a pre-heating process (pre-baking process), and a post-heating process (post-baking process).

The heating temperature in the preheating process is preferably 80 to 200°C, and more preferably 90 to 150°C. When a hot plate is used, the heating time in the pre-heating process is preferably 30 to 240 seconds.

The heating temperature in the post-heating process is preferably 120°C to 250°C, and more preferably 160°C to 220°C. When a hot plate is used, the heating time in the post-heating process is preferably 3 minutes to 180 minutes.

<Solid imaging element> The infrared light cut filter described above can be suitably applied to a solid-state imaging element. Hereinafter, an embodiment of the solid-state imaging element of the present invention will be described using FIG. 1. In the solid-state imaging element (infrared light sensor) 100 shown in FIG. 1, reference numeral 110 is a solid-state imaging element substrate. An infrared cut filter 111 and a color filter 112 are arranged on the solid-state imaging element substrate 110. An area 114 is provided between the infrared light transmission filter (color filter that transmits infrared light) 113 and the solid-state imaging element substrate 110. In the region 114, a resin layer (for example, a transparent resin layer or the like) through which light of the wavelength of the infrared light transmission filter 113 is transmitted is arranged. An infrared light transmission filter 113 may be formed in the area 114. That is, the infrared light transmission filter 113 can be formed on the solid-state imaging element substrate 110. A microlens 115 is arranged on the incident light hν side of the color filter 112 and the infrared light transmission filter 113. A planarization layer 116 is formed so as to cover the microlens 115. In FIG. 1, the film thickness of the color filter 112 and the film thickness of the infrared light transmission filter 113 are the same, but the film thickness of the two may also be different. In FIG. 1, the color filter 112 is disposed closer to the incident light hν side than the infrared light cut filter 111, but the order of the infrared light cut filter 111 and the color filter 112 may be replaced to cut off infrared light. The filter 111 is provided closer to the incident light hν side than the color filter 112. Other layers may be formed between the infrared light cut filter 111 and the color filter 112. As the color filter 112, it is selected from the group consisting of a color filter that transmits light in the red wavelength region, a color filter that transmits light in the green wavelength region, and a color filter that transmits light in the blue wavelength region. At least one of them is preferred. In addition, an infrared light absorbing substance may be included in the color filter 112 to make the color filter 112 function as an infrared light cut filter.

The solid-state imaging element of the present invention has an infrared cut-off filter inside, so the infrared cut-off filter that is a component of the camera module is not needed, and the number of components of the camera module can be reduced, thereby enabling miniaturization of the camera module .

The color filter 112 is not particularly limited, and a conventionally known color filter for pixel formation can be used. For example, the descriptions in paragraphs 0214 to 0263 of Japanese Patent Application Laid-Open No. 2014-043556 can be referred to, and the contents thereof are incorporated in the specification of the present application. The infrared light transmission filter 113 selects its characteristics according to the emission wavelength of its light source.

As one of the preferred aspects of the solid-state imaging device, a color filter (red color filter) including light selected from a wavelength region that transmits red light and a color filter (green color filter) that transmits light in a green wavelength region are provided Filter), at least one filter layer and arrangement in the group of a color filter (blue filter) that transmits light in the blue wavelength region and a color filter (infrared light transmission filter) that transmits infrared light An infrared light cut filter located closer to the light incident side than the filter layer is preferred. For example, a filter layer having a red color filter, a green color filter, a blue color filter, and an infrared light transmission filter on the same plane, and a position closer to the light incident side than the filter layer can be given The solid-state imaging element of the infrared cut-off filter is arranged on the entire filter layer. In addition, the infrared light cut filter may be disposed on the light incident side of the substrate 110. For example, an infrared light cut filter may be arranged on the red filter, a green filter, and a blue filter, and an infrared light cut filter may be arranged on the infrared light transmission filter. In addition, a flattening layer may be arranged between the filter layer and the infrared light cut filter.

Next, as an example to which the solid-state imaging element of the present invention is applied, an imaging device (camera system) will be described. FIG. 2 is a functional block diagram of an imaging device. The imaging device includes a lens optical system 1, a solid-state imaging element 10, a signal processing section 20, a signal switching section 30, a control section 40, a signal accumulation section 50, a light emission control section 60, and an infrared LED (light emitting diode) of a light emitting element that emits infrared light (Light Emitting Diode) 70 and image output sections 80 and 81. In addition, as the solid-state imaging element 10, the above-described solid-state imaging element 100 can be used. In addition, all or a part of the configurations other than the solid-state imaging element 10 and the lens optical system 1 can be formed on the same semiconductor substrate. For each configuration of the imaging device, refer to paragraphs 0032 to 0036 of Japanese Patent Laid-Open No. 2011-233983, the contents of which are incorporated in the specification of this application. As the imaging device, there are a motion sensor, a proximity sensor, a gesture sensor, and the like. [Example]

Hereinafter, the embodiments of the present invention will be described, but the present invention is not limited by these embodiments. In addition, unless otherwise specified, "parts" and "%" are quality standards.

<Preparation of composition (photosensitive composition)> The photosensitive composition was prepared by dissolving the components shown in Table 1 below in the solvents shown in the table.

[Table 1]

The following summarizes the various components used in Table 1 above.

(Resin adhesive) Resin A: Acrycure RD-F8 manufactured by NIPPON SHOKUBAI CO., LTD. (conforming to alkali-soluble adhesives with double bond groups) (Polymerizable compound) DPHA: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) (Polymerization initiator) IRGACURE 369: IRGACURE 369 (made by BASF) (Sensitizer) DETX-S: Kayacure DETX-S (2,4-diethylthioxanthone) (manufactured by SHOJI SANGYO Co., Ltd.) (Solvent) PGMEA: 1-methoxy-2-propanol acetate (Surfactant) Megafac F-781-F (manufactured by DIC Corporation)

(UV absorber (ultraviolet absorber))

[Chemical Formula 9]

In addition, the results of the thermal mass measurement of the above UV1 to UV-6 are shown in Table 2 below.

[Table 2]

(Polymerization inhibitor)

[Chemical Formula 10]

(Specific particles) Specific particles 1 were produced in the following steps. After stirring a mixture of tungsten microparticles (composition: Cs _0.33 WO ₃ , average particle diameter: 20 nm) (100 parts by mass), ethyl silicate (10 parts by mass), and methanol (90 parts by mass) at 0°C for 10 hours, Stirred at 20°C for 20 hours. The solid content was filtered from the resulting mixture, and the recovered solid content was dried at 25°C for 24 hours, at 100°C for 10 hours, and at 200°C for 1 hour, followed by pulverization to obtain specific particles 1. (Tungsten particles coated with SiO ₂ ). As shown in Table 3 described later, except for changing the type of coupling agent, the specific particles 2 to 4 were produced in the same procedure as described above. The specific particles 2 are tungsten particles coated with TiO ₂ , the specific particles 3 are tungsten particles coated with Al ₂ O ₃ , and the specific particles 4 are tungsten particles coated with ZrO ₂ . In addition, the tungsten fine particles that have not been coated as described above are designated as the specific particles 5.

[table 3]

In addition, the above composition further contains a dispersant. The dispersant has the function of dispersing the above-mentioned specific particles.

The following various measurements were performed using the composition obtained above. The results are summarized in Table 5 below.

<Evaluation of heat resistance> After mixing the raw materials shown in Table 4 below at the ratio (parts by mass) shown in Table 4, it was filtered with a nylon filter (manufactured by Nihon Pall Ltd.) with a pore size of 0.45 μm to prepare a Green composition. Red (red) composition and Blue (blue) composition. In addition, the numerical values in the table represent parts by mass.

[Table 4]

In addition, the pigment dispersion liquid 1 is a composition containing the following components. ・C.I. Pigment Green 58...... 11.4 parts by mass ・C.I. Pigment Yellow 185......2.3 parts by mass ・Compound 1 of the following structure...1.4 parts by mass

[Chemical Formula 11]

・Dispersant 1 (resin of the following structure (acid value = 49 mgKOH/g, Mw = 24000, the value attached to the main chain is the molar ratio.)) 7.2 parts by mass

[Chemical Formula 12]

・Propylene glycol methyl ether acetate......81.9 parts by mass

Pigment dispersion 2 is a composition containing the following components. ・C.I. Pigment Red 254...... 11.4 parts by mass ・C.I. Pigment Yellow 139......2.3 parts by mass ・Compound 1 of the above structure...1.4 parts by mass ・The above dispersant 1...7.2 parts by mass ・Propylene glycol methyl ether acetate......77.77 parts by mass

The pigment dispersion liquid 3 is a composition containing the following components. ・C.I. Pigment Blue 15:6...11.4 parts by mass ・C.I. Pigment Violet 23...2.3 parts by mass ・Compound 1 of the above structure...1.4 parts by mass ・The above dispersant 1...7.2 parts by mass ・Propylene glycol methyl ether acetate......81.9 parts by mass

・Resin A: Resin of the following structure (acid value = 70 mgKOH/g, Mw = 11000, and the value appended to the main chain is the molar ratio. Use paragraphs 0304 to 0307 of Japanese Patent Laid-Open No. 2012-173356 Method was synthesized.)

[Chemical Formula 13]

・Single A: M-350 (TOAGOSEI CO., LTD.) ・Photopolymerization initiator 1: IRGACUREOXE03 (BASF Corporation) ・Photopolymerization initiator 2: IRGACUREOXE04 (BASF Corporation) ・Polymerization inhibitor: p-methoxyphenol ・Organic solvent: PGMEA ・Epoxy compound: EHPE-3105 (Daicel Chemical Industries, Ltd.) ・Surfactant: Megafac-781F (DIC Corporation)

The photosensitive composition of Example 1 was applied on a glass wafer by spin coating so that the film thickness after film formation became 2.7 μm, and then heated on a hot plate at 100° C. for 2 minutes. Then, using an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), the obtained coating film was fully exposed at 1000 mJ/cm ² , and further heated on a hot plate at 220° C. for 5 minutes to obtain Hardened layer. Next, the green composition was applied on the hardened layer by a spin coating method so that the film thickness after film formation became 1.5 μm, and then heated on a hot plate at 100° C. for 2 minutes. Then, using an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), the obtained coating film was fully exposed at 1000 mJ/cm ² , and further heated on a hot plate at 220° C. for 5 minutes, and A green film was laminated on the hardened layer to obtain a sample G1 including the hardened layer and the green film. Instead of the Green composition, a Red composition or a Blue composition was used to obtain a sample R1 containing a hardened layer and a Red film, and a sample containing a hardened layer and a Blue film B1. In the above, instead of the photosensitive composition of Example 1, the photosensitive compositions of other examples and comparative examples were used to prepare various samples.

Using an ultraviolet-visible-near infrared spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation), the light transmittance of the obtained sample was measured in the wavelength range of 400 to 1300 nm. Next, the obtained sample was heated on a hot plate at 240° C. for 300 seconds, and the change in transmittance (ΔT) in the wavelength range of 400 to 1300 nm before and after heating was measured as an index of heat resistance. The smaller the value of ΔT, the better the heat resistance, and the criterion is as follows. In addition, the above ΔT represents a change in transmittance at a wavelength that shows the maximum change in transmittance in the wavelength range of 400 to 1300 nm. Practically, A or B is preferred. "A": ΔT＜2% "B": 2%≤ΔT%<5% "C": ΔT%≥5% In addition, the results of each sample formed using the Green (red) composition, the Red (red) composition, and the Blue (blue) composition are shown in Table 5 described below.

<Evaluation of pattern rectangularity> After applying the photosensitive compositions of each example and comparative example on a silicon substrate and drying at 100° C. for 2 minutes, the exposure device UX3100-SR (manufactured by Ushio Inc.) was used to pass The light mask (mask pattern: 50 μm line and gap) was irradiated with light (exposure amount: 100-2000 mJ/cm ² ). Using a 60% aqueous solution of organic alkaline developer CD-2000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.), the pattern-exposed coating film was spin-immersed and developed at room temperature for 60 seconds. The shower was rinsed with pure water for 20 seconds. Then, it was washed with pure water. Then, the water droplets were flown out with high-pressure air to naturally dry the substrate, and post-baking treatment was performed on a hot plate at 220° C. for 300 seconds to form a cured film (thickness: 2.7 μm) as a line portion. The rectangularity was evaluated by the obtained cross-sectional evaluation of the line portion. Specifically, as shown in FIG. 3, the value of the angle θ formed by the line portion 202 with respect to the silicon substrate 200 was obtained, and the evaluation was performed according to the following criteria. Practically, A or B is preferred. “A”: θ is 80-100° “B”: θ is 70° or more and less than 80° or more than 100° and less than 110° “C”: θ is less than 70° or more than 110°

[table 5]

As shown in Table 5 above, when the photosensitive composition of the present invention is used, predetermined effects are obtained. Among them, as shown in Examples 1 to 9, in the thermal mass measurement of the ultraviolet absorber, when the mass reduction rate at 150°C is 5% or less and the mass reduction rate at 220°C is 40% or more, heat resistance Excellent. As shown in Examples 2 to 9, in the thermal mass measurement of the ultraviolet absorber, when the mass reduction rate at 150°C is 5% or less and the mass reduction rate at 220°C exceeds 40%, heat resistance is particularly excellent .

In addition, in Example 6, the resin A was replaced with the resin B (the following structure) as a binder, except that a photosensitive composition was prepared and subjected to various evaluations in the same procedure. As a result, Example 6 has the same result. Resin B: The following structure. (Acid value=95mgKOH/g, Mw=41000, the value attached in the main chain is the molar ratio.)

[Chemical Formula 14]

In Example 6, the resin A was replaced with a mixture of resin A and resin C (the following structural formula) as a binder (resin A/resin C=7.85/7.85), except that the photosensitive was prepared in the same manner Various evaluations were performed on the sexual composition, and as a result, the same results as in Example 6 were obtained. Resin C: The following structure. (Acid value = 217mgKOH/g, Mw = 11000, the value attached to the main chain is the molar ratio.)

[Chemical Formula 15]

In Example 6, except that DPHA was replaced with ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.) as a polymerizable compound, a photosensitive composition was prepared in the same manner and various evaluations were carried out, as a result , The same results as in Example 6 were obtained.

In Example 6, except that DPHA was replaced with DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, a photosensitive composition was prepared in the same manner and various evaluations were performed, as a result , The same results as in Example 6 were obtained.

In Example 6, except that DPHA was replaced with OGSOL EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd.) as a polymerizable compound, a photosensitive composition was prepared in the same manner and various evaluations were performed, except that As a result, the same results as in Example 6 were obtained.

In Example 6, DPHA was replaced with a mixture of DPHA and ARONIX M-510 (DPHA: ARONIX M-510 (mass ratio) = 1:1) as the polymerizable compound, except that the photosensitive was prepared in the same manner Various evaluations were carried out on the composition, and as a result, the pattern rectangularity was more excellent than in Example 6. From this result, it is considered that the pattern rectangularity is further improved by using two or more kinds of polymerizable compounds.

In Example 6, except that IRGACURE369 was replaced by IRGACUREOXE01 (manufactured by BASF) as an initiator, a photosensitive composition was prepared in the same manner and subjected to various evaluations. As a result, the pattern rectangularity was higher than in the example 6 is even better. Based on this result, it is considered that the pattern rectangularity is further improved by using an oxime compound (oxime-based initiator).

In Example 6, except that IRGACURE369 was replaced with IRGACUREOXE03 (manufactured by BASF) as an initiator, a photosensitive composition was prepared in the same manner and subjected to various evaluations. As a result, the pattern rectangularity was higher than in the example 6 is even better. Based on this result, it is considered that the pattern rectangularity is further improved by using an oxime compound (oxime-based initiator).

In Example 6, except that IRGACURE369 was replaced by IRGACUREOXE04 (manufactured by BASF Corporation) as the initiator, the photosensitive composition was prepared and subjected to various evaluations in the same manner. As a result, the pattern rectangularity was higher than in the example. 6 is even better. Based on this result, it is considered that the pattern rectangularity is further improved by using an oxime compound (oxime-based initiator).

In Example 6, IRGACURE369 was replaced with a mixture of IRGACURE369 and IRGACUREOXE04 (IRGACURE369: IRGACUREOXE04 (mass ratio) = 0.75:0.75) as an initiator, except that a photosensitive composition was prepared and carried out in the same manner As a result of various evaluations, the pattern rectangularity was more excellent than in Example 6. Based on this result, it is considered that the pattern rectangularity is further improved by using an oxime compound (oxime-based initiator).

In Example 6, except that the sensitizer was not used, the photosensitive composition was prepared in the same manner and subjected to various evaluations. As a result, the same results were obtained except that the pattern rectangularity became B. It is believed that by using a sensitizer, the rectangularity of the pattern is further improved.

In Example 6, except that no surfactant was used, a photosensitive composition was prepared in the same manner and various evaluations were carried out. As a result, the same results were obtained except that the pattern rectangularity became B. It is thought that by using a surfactant, the rectangularity of the pattern is further improved.

In Example 6, instead of using ethylene glycol monobutyl ether acetate, but butyl acetate was used, a photosensitive composition was prepared in the same manner and various evaluations were carried out. 6 The same result.

In Example 6, except for using PGMEA instead of butyl acetate, a photosensitive composition was prepared in the same manner and subjected to various evaluations. As a result, the same results as in Example 6 were obtained.

1‧‧‧Lens optical system 10‧‧‧Solid image sensor 20‧‧‧Signal Processing Department 30‧‧‧Signal switching section 40‧‧‧Control Department 50‧‧‧Signal accumulation department 60‧‧‧Light Control 70‧‧‧Infrared LED 80、81‧‧‧Image output section 100‧‧‧Solid camera element 110‧‧‧Solid imaging element substrate 111‧‧‧Infrared cut filter 112‧‧‧ color filter 113‧‧‧Infrared light transmission filter 114‧‧‧Region 115‧‧‧Microlens 116‧‧‧Planning layer 200‧‧‧Si substrate 202‧‧‧ Line Department hν‧‧‧incident light

FIG. 1 is a schematic cross-sectional view showing the configuration of an embodiment of the solid-state imaging element of the present invention. 2 is a functional block diagram of an imaging device to which the solid-state imaging element of the present invention is applied. FIG. 3 is a diagram for explaining pattern rectangularity evaluation.

Claims (12)

A photosensitive composition containing metal-containing tungsten oxide particles, a polymerizable compound, a polymerization initiator, an ultraviolet absorber, and a polymerization inhibitor, in the photosensitive composition The mass ratio of the content of the ultraviolet absorber to the content of the polymerization inhibitor is 0.08 to 330. The photosensitive composition according to claim 1, wherein The surface of the metal-containing tungsten oxide particles is coated with metal oxide. The photosensitive composition according to claim 2, wherein The metal oxide is an oxide of at least one element selected from the group consisting of Si, Ti, Zr, and Al. The photosensitive composition according to any one of claims 1 to 3, wherein This ultraviolet absorber is an ultraviolet absorber having a mass reduction rate at 150°C of 5% or less and a mass reduction rate at 220°C of 40% or more in thermal mass measurement. The photosensitive composition according to any one of claims 1 to 3, wherein The ultraviolet absorber is at least one selected from the group consisting of dibenzoylmethane-based compounds and aminobutadiene-based compounds. The photosensitive composition according to any one of claims 1 to 3, which contains two or more kinds of the polymerization inhibitors. The photosensitive composition according to claim 6, wherein The polymerization inhibitor is at least two or more selected from the group consisting of hindered phenol compounds, phenol compounds other than the hindered phenol compounds, benzoquinone compounds, and hydroquinone compounds. The photosensitive composition according to claim 7, wherein The polymerization inhibitor includes one or more first polymerization inhibitors selected from the group consisting of the hindered phenol compound, the benzoquinone compound, and the hydroquinone compound, and phenol compounds other than the hindered phenol compound . The photosensitive composition according to claim 8, wherein The mass ratio of the content of the phenol compound other than the hindered phenol compound to the total content of the first polymerization inhibitor is 0.0009 to 0.17. The photosensitive composition according to any one of claims 1 to 3, further comprising an alkali-soluble binder having a double bond group. An infrared light cut filter formed using the photosensitive composition according to any one of claims 1 to 10. A solid-state imaging element comprising the infrared light cut filter described in claim 11.

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