TW201837042A - Composition for solid-state imaging element, infrared shielding film, and solid-state imaging element having both good visible light transmittance and infrared shielding properties - Google Patents

Abstract

The present invention provides a composition for a solid-state imaging element which can form an optical filter for a solid-state imaging element having both good visible light transmittance and infrared shielding properties, even when the types of organic dye to be contained are small. The present invention is a composition for a solid-state imaging element comprising a phthalocyanine compound represented by the following formula (1). In the formula (1), a plurality of Rs are each independently an alkyl group or an aryl group. A plurality of Xs are each independently a hydrogen atom, a halogen atom or an alkyl group. The plurality of Xs may also be bonded to one another and form an aromatic ring with these bonded carbon chains. M is a derivative of two hydrogen atoms, a divalent metal atom or a trivalent or tetravalent metal atom. A plurality of ns are each independently an integer of 3 to 6.

Description

Composition for solid-state imaging device, infrared shielding film, and solid-state imaging device

The present invention relates to a composition for a solid-state imaging device, an infrared shielding film, and a solid-state imaging device.

A Charge-Coupled Device (CCD) image sensor or a Complementary Metal Oxide Semiconductor (CMOS) image sensor is mounted on a camera, a digital camera, a mobile phone with a camera function, and the like. Solid-state imaging element. The sensitivity of the photodiode provided in the solid-state imaging device spans the visible light region to the infrared region. Therefore, in the solid-state imaging element, a filter for blocking infrared rays is provided. By the infrared ray interrupting filter, the sensitivity of the solid-state imaging element can be corrected in such a manner that the human visual sensitivity is approached.

A dye or a pigment as an infrared shielding agent is contained in the infrared ray blocking filter. The infrared shielding agent is required to sufficiently penetrate visible light and absorb infrared rays. A phthalocyanine compound has been studied as one of the infrared shielding agents, particularly a good shielding agent for near-infrared rays (refer to Japanese Laid-Open Patent Publication No. 2008-201952).

However, in the conventional infrared ray blocking filter using a phthalocyanine compound, the visible light transmittance and the infrared ray shielding property are not sufficiently satisfied. Therefore, in order to exhibit good characteristics, for example, a plurality of infrared shielding agents may be used in combination. The use of the various infrared shielding agents also causes a high cost and a decrease in productivity. Further, in the conventional infrared ray interrupting filter using the phthalocyanine compound, the variation in the transmittance in the visible light region may be large. In this case, no good visual acuity correction was performed. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-201952

[Problems to be Solved by the Invention] However, in the infrared ray interrupting filter for a solid-state imaging device using a phthalocyanine compound, the visible light transmittance and the infrared ray shielding property are not sufficiently satisfied. Therefore, in order to exhibit good characteristics, for example, a plurality of infrared shielding agents may be used in combination. The use of the various infrared shielding agents also causes a high cost and a decrease in productivity. Further, in the conventional infrared ray interrupting filter using the phthalocyanine compound, the variation in the transmittance in the visible light region may be large. In this case, no good visual acuity correction was performed.

The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide a solid-state imaging device, a solid-state imaging device having the infrared shielding film, and a composition for the solid-state imaging device. In other words, when the type of the organic dye to be contained is small, an optical filter for a solid-state imaging device having excellent visible light transmittance and infrared shielding properties can be formed, and the infrared shielding film for the solid-state imaging device can be used even if When the type of the organic dye contained is small, it also has good visible light transmittance and infrared shielding properties. [Means for solving the problem]

In order to solve the problem, the invention is a composition for a solid-state image sensor, which comprises a phthalocyanine compound represented by the following formula (1) (hereinafter also referred to as "[A] phthalocyanine compound"). [Chemical 1] (In the formula (1), a plurality of R are each independently an alkyl group or an aryl group. The plurality of X are each independently a hydrogen atom, a halogen atom or an alkyl group. A plurality of X may be bonded to each other and bonded thereto. The carbon chains of the knot together form an aromatic ring. M is a derivative of two hydrogen atoms, a divalent metal atom or a trivalent or tetravalent metal atom. The plurality of n are each independently an integer of 3 to 6)

Another invention completed to solve the above problems is an infrared shielding film (I) formed of the composition for a solid-state imaging device.

Still another invention completed in order to solve the above problem is an infrared shielding film (II) for a solid-state imaging device, which substantially contains only one or two kinds of organic dyes, and satisfies the following (A) to (C). (A) The average value of the transmittance in the range of 430 nm or more and 580 nm or less is 75% or more (B) The average value of the transmittance in the range of 700 nm and 900 nm or less is 16.5% or less ( C) The transmittance at a wavelength of 1200 nm is 10% or less

Still another invention completed to solve the above problems is a solid-state imaging element including the infrared ray shielding film (I) or the infrared ray shielding film (II). [Effects of the Invention]

According to the present invention, there is provided a composition for a solid-state imaging device, an infrared shielding film for a solid-state imaging device, and a solid-state imaging device including the infrared shielding film, and the composition for the solid-state imaging device is even if it contains an organic dye When the type is small, an optical filter for a solid-state imaging device having excellent visible light transmittance and infrared shielding properties can be formed, and the infrared shielding film for a solid-state imaging device has a small amount of organic dye contained therein. In the case of both, it also has good visible light transmittance and infrared shielding properties.

Hereinafter, the composition for a solid-state imaging device, the infrared shielding film, and the solid-state imaging device according to the embodiment of the present invention will be described in detail.

<Composition for Solid-State Imaging Device> The composition for a solid-state imaging device according to the embodiment of the present invention (hereinafter also simply referred to as "composition") contains the [A] phthalocyanine compound. The composition preferably further contains [B] an infrared shielding agent, and the [B] infrared shielding agent is a metal oxide, a copper compound (excluding the [A] phthalocyanine compound), or a combination thereof.

([A] Phthalocyanine compound) [A] The phthalocyanine compound is a compound represented by the following formula (1). [A] The visible light region of the phthalocyanine compound (for example, a wavelength region of 430 nm or more and 580 nm or less) has high permeability, and on the other hand, the near-infrared region (for example, a wavelength region of 700 nm or more and 900 nm or less) is shielded. High sex. Since the composition contains the [A] phthalocyanine compound, an optical filter having both good visible light transmittance and infrared shielding properties can be formed even when the type of the organic dye contained is small. Further, since the composition contains the [A] phthalocyanine compound, it is possible to form an optical filter having high uniform permeability in the visible light region.

[Chemical 2]

In the formula (1), the plurality of R are each independently an alkyl group or an aryl group. The plurality of X are each independently a hydrogen atom, a halogen atom or an alkyl group. A plurality of Xs may also be bonded to each other and form an aromatic ring together with the bonded carbon chains. M is a derivative of two hydrogen atoms, a divalent metal atom or a trivalent or tetravalent metal atom. The plurality of n are each independently an integer of 3 to 6.

Examples of the alkyl group represented by R include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, a t-butyl group, and the like. A linear or branched alkyl group having 1 to 30 carbon atoms.

Examples of the aryl group represented by R include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and an anthracenyl group.

The R is preferably an alkyl group, more preferably a linear or branched alkyl group having 1 to 12 carbon atoms. Further, the upper limit of the carbon number of the alkyl group is preferably 6, more preferably 4, and still more preferably 2. As the R, a methyl group is particularly preferable.

Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, and a bromine atom.

The alkyl group represented by the above X is exemplified as the alkyl group represented by the above R.

A plurality of Xs may also be bonded to each other. Generally, in a plurality of X, two X bonds bonded to the same benzene ring are bonded to each other, and together with the bonded carbon chains form an aromatic ring. Examples of the aromatic ring to be formed include a benzene ring, a naphthalene ring, an anthracene ring and the like. The hydrogen atoms of the aromatic rings may also be substituted by a hydrocarbon group or other substituents.

As the X, a hydrogen atom is preferred.

Examples of the divalent metal atom represented by the above-mentioned M include Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, Ru, Rh, and Pb. Further, the divalent metal atom means a metal atom which can be a divalent cation.

Here, the derivative of a metal atom means an atomic group containing a metal atom. The trivalent metal atom means a metal atom which can be a trivalent cation. Examples of the trivalent metal atom include Al, In, and the like. The tetravalent metal atom means a metal atom which can be a tetravalent cation. Examples of the tetravalent metal atom include Si, Ge, and Sn. Furthermore, the metal atom also contains a semi-metal atom. Examples of the derivative of the trivalent or tetravalent metal atom represented by M include AlCl, AlBr, AlI, AlOH, InCl, InBr, InI, InOH, SiCl ₂ , SiBr ₂ , SiI ₂ , Si(OH). _{2, GeCl 2, GeBr 2,} GeI 2, SnCl 2, SnBr 2, SnI 2, Sn (OH) 2, VO, TiO and the like.

As the M, preferably H ₂ (two hydrogen atoms), Pd, Cu, Zn, Pt, Ni, Co, Fe, Mn, Sn, In, SnCl ₂ , AlCl, VO, and TiO, more preferably VO .

The lower limit of the n is preferably 4. The upper limit of the n is preferably 5, more preferably 4.

The lower limit of the maximum absorption wavelength of the [A] phthalocyanine compound is preferably 680 nm, more preferably 700 nm, and further preferably 720 nm. On the other hand, the upper limit of the maximum absorption wavelength is preferably 1,000 nm, more preferably 900 nm, further preferably 800 nm, and even more preferably 750 nm. When the maximum absorption wavelength of the [A] phthalocyanine compound is within the above range, an optical filter having better visible light transmittance and infrared shielding properties can be formed.

The method for synthesizing the [A] phthalocyanine compound is not particularly limited, and a known method can be combined and synthesized. For example, it can be synthesized according to the following scheme (scheme) 1.

[Chemical 3]

In the scheme 1, R, X, M and n have the same meanings as in the formula (1).

Further, as the dicyano compound in the scheme 1, a plurality of dicyano compounds having different substituents (RO(CH ₂ ) _n - or X) may be used. Examples of the supply source of the metal ion or the like represented by M ²⁺ include various metal salts such as acetate, chloride, bromide, nitrate, and sulfate. The [A] phthalocyanine compound represented by the above formula (1) can be obtained by mixing the compound represented by the formula (0) with a metal salt in a solvent. Examples of the solvent include aromatic hydrocarbons (such as benzene and toluene), aliphatic hydrocarbons (such as hexane and cyclohexane), and chlorinated hydrocarbons (such as dichloromethane, chloroform, and dichloroethane). Dimethyl Formamide (DMF), dimethylsulfoxide (DMSO), acetonitrile, tetrahydrofuran (THF), N-methylpyrrolidone, dioxane, alcohol (methanol, ethanol, etc.) Wait.

The lower limit of the content of the [A] phthalocyanine compound in the total solid content of the composition is preferably 0.1% by mass, more preferably 0.5% by mass, still more preferably 1% by mass. On the other hand, the upper limit of the content is preferably 30% by mass, more preferably 15% by mass, still more preferably 10% by mass, still more preferably 5% by mass. By setting the content of the [A] phthalocyanine compound within the above range, the obtained optical filter has a better balance between visible light transmittance and infrared shielding property.

[A] The phthalocyanine compound may be used alone or in combination of two or more. Among them, it is preferred to use only one or two kinds of [A] phthalocyanine compounds, and it is more preferred to use only one [A] phthalocyanine compound. [A] The phthalocyanine compound can exhibit good visible light transmittance and infrared shielding properties using only one type. Therefore, by reducing the number of types of use of the [A] phthalocyanine compound, it is possible to exhibit good visible light transmittance and infrared shielding properties, and to improve productivity.

([B] Infrared masking agent) [B] The infrared shielding agent is a metal oxide, a copper compound (except [A] phthalocyanine compound), or a combination of these. As the [B] infrared shielding agent, a compound having a maximum absorption wavelength in a range of 800 nm or more and 2000 nm or less is preferable. By using the [B] infrared shielding agent in combination with the [A] phthalocyanine compound, the infrared shielding performance of the obtained optical filter is further improved.

Examples of the metal oxide as the [B] infrared shielding agent include a tungsten oxide compound, quartz (SiO ₂ ), magnetite (Fe ₃ O ₄ ), alumina (Al ₂ O ₃ ), and titania (TiO). ₂ ), zirconium oxide (ZrO ₂ ), spinel (MgAl ₂ O ₄ ), and the like.

The copper compound as the [B] infrared shielding agent may, for example, be a copper phthalocyanine compound or another copper complex. Examples of the copper phthalocyanine-based compound include copper phthalocyanine, copper chloride phthalocyanine, copper bromide phthalocyanine, and copper bromide phthalocyanine.

The [B] infrared shielding agent is preferably a metal oxide, more preferably a tungsten oxide compound. The tungsten oxide-based compound is an infrared shielding agent which has high absorption of ultraviolet rays (especially, infrared rays having a wavelength of about 800 nm or more and 1200 nm or less) (that is, high shielding properties against infrared rays) and low absorption of visible light. Therefore, by containing the tungsten oxide-based compound in the composition, it is possible to maintain good visible light transmittance of the obtained optical filter and improve infrared shielding properties. [B] The infrared shielding agent may be used singly or in combination of two or more.

The tungsten oxide-based compound is more preferably a tungsten oxide-based compound represented by the following formula (2). A _x WO _y ···(2)

In the formula (2), A is a metal element. 0.001 ≦ x ≦ 1.1. 2.2 ≦ y ≦ 3.0.

Examples of the metal element represented by A in the formula (2) include an alkali metal, an alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, and Pt. Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and the like. The metal element represented by A may be one type or two or more types.

The above A is preferably an alkali metal, more preferably Rb and Cs, and still more preferably Cs. That is, the metal oxide is more preferably tungsten oxide.

When x in the above formula (2) is 0.001 or more, infrared rays can be sufficiently shielded. The lower limit of x is preferably 0.01, more preferably 0.1. On the other hand, when x is 1.1 or less, it is possible to more reliably prevent the formation of an impurity phase in the tungsten oxide-based compound. The upper limit of x is preferably 1, more preferably 0.5.

By the y in the formula (2) being 2.2 or more, the chemical stability as a material can be further improved. The lower limit of y is preferably 2.5. On the other hand, by y being 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the tungsten oxide-based compound represented by the formula (2) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 ,} etc., preferably Cs _0.33 WO ₃ and Rb. _0.33 WO ₃ , and thus preferably Cs _0.33 WO ₃ .

[B] The infrared shielding agent is preferably fine particles. The upper limit of the average particle diameter (D50) of the [B] infrared shielding agent is preferably 500 nm, more preferably 200 nm, still more preferably 50 nm, and still more preferably 30 nm. When the average particle diameter is not more than the above upper limit, the visible light transmittance can be further improved. On the other hand, the average particle diameter of the [B] infrared shielding agent is usually 1 nm or more, and may be 10 nm or more, for reasons such as ease of handling during production.

[B] The infrared shielding agent can also be synthesized by a known method, and can be obtained as a commercial item. In the case where the metal oxide is, for example, a tungsten oxide-based compound, the tungsten oxide-based compound can be obtained, for example, by a method of heat-treating a tungsten compound in an inert gas atmosphere or a reducing gas atmosphere. In addition, the tungsten oxide-based compound can be obtained, for example, as a dispersion of tungsten fine particles such as "YMF-02" by Sumitomo Metal Mining Co., Ltd.

The lower limit of the content of the [B] infrared shielding agent in the total solid content of the composition is preferably 1% by mass, more preferably 5% by mass, and still more preferably 10% by mass. The lower limit of the content is more preferably 20% by mass, still more preferably 30% by mass. On the other hand, the upper limit of the content is preferably 70% by mass, more preferably 65% by mass, and still more preferably 60% by mass. By setting the content of the [B] infrared shielding agent to the above range, the obtained optical filter has a better balance between visible light transmittance and infrared shielding property.

The lower limit of the mass ratio of the [B] infrared shielding agent to the content of the [A] phthalocyanine compound ([B]/[A]) is preferably 2, preferably 3, and more preferably 5, and further More preferably 10. On the other hand, as the upper limit of the mass ratio ([B]/[A]), it is preferably 40, more preferably 30, and still more preferably 20. By setting the content ratio of the [A] phthalocyanine compound to the [B] infrared shielding agent to be within the above range, the obtained optical filter has a better balance between visible light transmittance and infrared shielding property.

([C] Dispersant) The composition preferably further contains a [C] dispersant. By the [C] dispersant, the uniform dispersibility of the [B] infrared shielding agent (especially a metal oxide) can be improved, and the visible light transmittance and infrared shielding property of the obtained optical filter can be further improved.

Examples of the [C] dispersant include an urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, and a polyoxyethylene alkyl phenyl ether dispersant. A polyethylene glycol diester dispersing agent, a sorbitan fatty acid ester dispersing agent, a polyester dispersing agent, a (meth)acrylic dispersing agent, or the like. Among these, a (meth)acrylic dispersant is preferred. The [C] dispersant is preferably a block copolymer.

[C] Dispersants are commercially available, for example, (meth)acrylic dispersants include Disperbyk-2000, Disperbyk-2001, BYK- LPN6919, BYK-LPN21116, BYK-LPN22102 (above is BYK), and the urethane dispersant can be listed as Disperbyk-161. , Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Despabike (Disperbyk) 182, Disperbyk-2164 (above made by BYK), Solsperse 76500 (manufactured by Lubrizol) Examples of the polyethylenimine dispersant include Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), and polyester dispersants include Ajisper PB821 and Ajis. Ajisper PB822, Ajisper PB880, Ajisper PB881 (above Ajinomoto Fine Chemicals (Ajinomoto Fine-Techno) (shares) Corporation), in addition include BYK (BYK) -LPN21324 (BYK Chemie (BYK) Manufacturing Company) and the like.

The lower limit of the amine value of the [C] dispersant is preferably 10 mgKOH/g, more preferably 40 mgKOH/g, and still more preferably 80 mgKOH/g. On the other hand, as the upper limit of the amine value, it is preferably 300 mgKOH/g, more preferably 200 mgKOH/g, and still more preferably 150 mgKOH/g. By using a dispersant having the amine valence, the dispersibility of the [B] infrared ray shielding agent is improved, and the visible light transmittance and infrared ray shielding property of the obtained optical filter can be further improved. Further, the "amine price" is the number of mg of KOH equivalent to the HCl equivalent required to neutralize 1 g of the solid component of the dispersant.

The lower limit of the content of the [C] dispersant is preferably 5 parts by mass, more preferably 15 parts by mass, even more preferably 30 parts by mass, based on 100 parts by mass of the [B] infrared shielding agent. On the other hand, the upper limit of the content is preferably 200 parts by mass, more preferably 100 parts by mass, and still more preferably 60 parts by mass.

([D] Polymerizable Compound) The composition preferably further contains a [D] polymerizable compound. When the composition contains the [D] polymerizable compound, it can exhibit good curability, good heat resistance of the obtained optical filter, and the like. The [D] polymerizable compound means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. The [D] polymerizable compound is preferably a compound having two or more (meth)acrylinyl groups and a compound having two or more N-alkoxymethylamino groups, more preferably two or more. (Meth) propylene fluorenyl compound. [D] The polymerizable compound may be used alone or in combination of two or more.

Examples of the compound having two or more (meth) acrylonitrile groups include polyfunctional (meth) acrylates such as a reactant of an aliphatic polyhydroxy compound and (meth)acrylic acid, and a change in caprolactone. a polyfunctional (meth) acrylate, an alkylene oxide-modified polyfunctional (meth) acrylate, a polyfunctional amine group as a reactant of a (meth) acrylate having a hydroxyl group and a polyfunctional isocyanate A poly(meth)acrylate having a carboxyl group such as a formate (meth) acrylate or a reaction product of a (meth) acrylate having a hydroxyl group and an acid anhydride.

Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, or glycerin, trimethylolpropane, pentaerythritol, and A trivalent or higher aliphatic polyhydroxy compound such as pentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and Pentaerythritol penta (meth) acrylate, glycerin dimethacrylate, and the like. Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include a dibasic acid anhydride such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, or pyromellitic dianhydride. A tetrabasic acid dianhydride such as biphenyltetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride.

Specific examples of the compound having two or more (meth)acrylinyl groups include ω-carboxypolycaprolactone mono(meth)acrylate, ethylene glycol (meth)acrylate, and 1, 6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylic acid Ester, polypropylene glycol di(meth) acrylate, bisphenoxyethanol hydrazine di(meth) acrylate, dimethylol tricyclodecane di(meth) acrylate, 2-hydroxy-3-(A) Acryloxypropyl methacrylate, 2-(2'-vinyloxyethoxy)ethyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol III Methyl) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris(2-(methyl) propylene methoxyethyl) Phosphate ester, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol triacrylate, urethane (meth) acrylate compound, and the like.

Among the compounds having two or more (meth)acryl fluorenyl groups, polyfunctional (meth) acrylates are preferred, and polyfunctional groups having 3 or more and 10 or less (meth) acryl fluorenyl groups are more preferred. (Meth) acrylate. Specifically, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferred.

Examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N', N', N'', N''-hexa(alkoxymethyl) Melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoguanamine, N,N,N',N'-tetrakis(alkoxymethyl)acetylene urea, and the like.

The content of the [D] polymerizable compound is preferably 10 parts by mass, more preferably 200 parts by mass, even more preferably 500 parts by mass, per 100 parts by mass of the [A] phthalocyanine compound. On the other hand, the upper limit of the content is preferably 3,000 parts by mass, more preferably 2,000 parts by mass.

([E] Polymerization Initiator) The composition preferably contains [E] a polymerization initiator. The [E] polymerization initiator may, for example, be a photopolymerization initiator, a thermal polymerization initiator or the like, and is preferably a photopolymerization initiator. Thereby, the composition can be provided with photosensitivity (radial sensitivity). The photopolymerization initiator is a compound which generates an active species which initiates polymerization of the [D] polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray. [E] The polymerization initiator may be used alone or in combination of two or more.

Examples of the [E] polymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, an O-mercaptoquinone compound, a phosphonium salt compound, and a benzoin system. A compound, a benzophenone-based compound, an α-diketone-based compound, a polynuclear oxime-based compound, a diazo-based compound, a quinone imide sulfonate-based compound, or a phosphonium salt-based compound. Among these, a thioxanthone-based compound, an acetophenone-based compound, a biimidazole-based compound, a triazine-based compound, and an O-indenyl-based compound are preferable, and an O-indenyl-based compound is more preferable.

Examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 2,4. - Dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like.

Examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one and 2-benzyl-2-dimethyl Amino-1-(4-morpholinylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholine Phenyl phenyl) butan-1-one and the like.

Examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'. - bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichloro Phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and the like.

Further, in the case of using a biimidazole-based compound, it is preferred to use a hydrogen donor in combination in terms of improving the sensitivity. The "hydrogen donor" as used herein means a compound which can supply a hydrogen atom to a radical generated by a biimidazole compound by exposure. Examples of the hydrogen donor include a mercaptan hydrogen donor such as 2-mercaptobenzothiazole or 2-mercaptobenzoxazole; and 4,4'-bis(dimethylamino)benzophenone; An amine-based hydrogen donor such as 4'-bis(diethylamino)benzophenone.

Examples of the triazine-based compound include the compounds described in paragraphs [0063] to [0065] of JP-A-57-57096, and JP-A-2003-238898.

Examples of the O-indenyl lanthanide compound include 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoguanidinopurine), and ethyl ketone-1. -[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-acetamidopurine), ethyl ketone-1-[9-B -6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-1-(O-acetamidino), ethyl ketone-1-[ 9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene}-9H-carbazole-3 -yl]-1-(O-ethylindenyl) and the like. As a commercial product of an O-indenyl lanthanide compound, NCI-831, NCI-930 (above, manufactured by ADEKA Co., Ltd.), OXE-03, OXE-04 (above, BASF (above) BASF) company manufacturing) and so on.

In the case of using a photopolymerization initiator, a sensitizer may be used in combination. Examples of the sensitizer include 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, and 4-dimer. Ethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5- Bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethyl Amino) chalcone and the like.

The lower limit of the content of the polymerization initiator is preferably 1 part by mass, more preferably 5 parts by mass, per 100 parts by mass of the [D] polymerizable compound. On the other hand, the upper limit of the content is preferably 100 parts by mass, more preferably 20 parts by mass.

(Binder Resin) The composition may further contain a binder resin. The binder resin is not particularly limited, and is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as "carboxyl group-containing polymer") is preferred. Examples of the carboxyl group-containing polymer include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as "unsaturated monomer (1)") and other copolymerizable ethylenically unsaturated monomers. A copolymer of a volume (hereinafter also referred to as "unsaturated monomer (2)).

Examples of the unsaturated monomer (1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2-(methyl) propylene methoxyethyl] ester, and ω. - Carboxypolycaprolactone mono(meth)acrylate, p-vinylbenzoic acid, and the like.

Examples of the unsaturated monomer (2) include an N-position substituted maleimide such as N-phenylmaleimide or N-cyclohexylmaleimine, styrene, and α. -methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, an aromatic vinyl compound such as hydrazine, methyl (meth) acrylate, (methyl) N-butyl acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, polyethylene glycol ( Degree of polymerization 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate Ester, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane - 8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide of p-cumylphenol Modified (meth) acrylate, ( Glycidyl acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloxymethyl]oxetane, 3-[(methyl (meth) acrylate such as acryloxymethyl]-3-ethyloxetane, cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 ^2,6 ]癸Vinyl-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, vinyl ether such as 3-(vinyloxymethyl)-3-ethyloxetane, polystyrene, poly(methyl The methyl acrylate, the poly(meth) acrylate, and the polyoxymethane are equal to a macromonomer having a mono(meth)acryl fluorenyl group at the terminal of the polymer molecular chain.

Further, as the binder resin, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylonitrile group in a side chain can also be used. Further, polysiloxane or the like can also be used as the binder resin.

In the case where the composition contains a binder resin, the content of the binder resin is usually 10 parts by mass or more and 10,000 parts by mass or less based on 100 parts by mass of the [A] phthalocyanine compound.

(Additive) The composition may also contain various additives as needed.

Examples of the additive include a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomeration agent, a residue improving agent, and a developability improving agent.

Examples of the surfactant include a fluorine surfactant, an anthrone surfactant, and the like. The content of the surfactant is usually 0.01 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the [A] phthalocyanine compound.

Examples of the adhesion promoter include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, and N-(2-aminoethyl)-3. -Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-shrinkage Glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropane Methyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, and the like.

Examples of the antioxidant include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-t-butylphenol, and pentaerythritol tetra [3-(3,5). -di-t-butyl-4-hydroxyphenyl)propionate],3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)- Propyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxa-spiro[5.5]undecane, thiodiethylene bis[3-(3,5- Di-t-butyl-4-hydroxyphenyl)propionate] and the like. The content of the antioxidant is usually 0.01 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the [A] phthalocyanine compound.

Examples of the ultraviolet absorber include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxybenzophenone.

Examples of the anti-agglomeration agent include sodium polyacrylate.

Examples of the residue improving agent include malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, and 3-amino-1-propanol. 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, and the like.

Examples of the developability improver include succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene oxiranyl ethyl] ester, and ω. a carboxypolycaprolactone mono(meth)acrylate or the like.

(Other organic dyes, etc.) The composition may contain a known organic dye other than the organic pigment of the [A] phthalocyanine compound and the copper compound which is the [B] infrared shielding agent. Examples of the other organic dyes include a diimine compound, a squarylium ylide compound, a cyanine compound, a naphthalocyanine compound, a quartetene compound, an ammonium compound, an imine compound, an azo compound, an anthraquinone compound, and an anthracene. A porphyrin compound, a pyrrolopyrrole compound, an oxophthalocyanine compound, a ketoxime compound, a hexaphyrin compound or the like (excluding a copper atom). Further, a phthalocyanine compound other than the [A] phthalocyanine compound and the phthalocyanine compound as the [B] infrared shielding agent can also be used.

In addition, the [A] phthalocyanine compound is preferably used in combination with a phthalocyanine compound other than the [A] phthalocyanine compound (hereinafter also referred to as "[a] phthalocyanine compound"). The lower limit of the maximum absorption wavelength of the [a] phthalocyanine compound is preferably 600 nm, more preferably 650 nm, further preferably 700 nm, and sometimes 750 nm, and sometimes 800 nm. On the other hand, the upper limit of the maximum absorption wavelength of the [a] phthalocyanine compound is preferably 900 nm, more preferably 850 nm, and sometimes more preferably 800 nm, and sometimes 750 nm, sometimes It is also better to be 700 nm. The lower limit of the difference between the maximum absorption wavelength of the [A] phthalocyanine compound and the maximum absorption wavelength of the [a] phthalocyanine compound is preferably 10 nm, more preferably 30 nm, and sometimes 50 nm. On the other hand, as the upper limit of the difference, it is preferably 100 nm, more preferably 80 nm, and sometimes 50 nm. By using the phthalocyanine compound in combination, the visible light transmittance and the infrared ray shielding property of the obtained optical filter can be further improved. In addition, the visible light uniformity of the obtained optical filter can also be improved. Further, a phthalocyanine compound which is a copper compound which is a [B] infrared shielding agent is also contained in the [a] phthalocyanine compound. The [a] phthalocyanine compound may be exemplified by various phthalocyanine compounds previously known.

The lower limit of the content of the [A] phthalocyanine compound in all the organic dyes in the composition is preferably 50% by mass, more preferably 70% by mass, and still more preferably 80% by mass, and sometimes It is also preferably 90% by mass, and sometimes more preferably 99% by mass. As the organic dye, it is also preferred to contain substantially only the [A] phthalocyanine compound. This composition can improve productivity by reducing the content of other organic pigments in the manner described. In addition, the visible light uniformity of the obtained optical filter can be improved.

In addition, the number of the organic dyes to be contained in the composition is also included in the [A] phthalocyanine compound, preferably three or less, more preferably two or less, and even more preferably one. Even if the number of kinds of the organic dye contained therein is reduced as described above, the productivity can be improved, and the visible light uniformity of the obtained optical filter can be improved. In the case of using two or more types of organic dyes, it is preferred to use a combination of the [A] phthalocyanine compound and a phthalocyanine compound other than the [A] phthalocyanine compound.

(Solvent) This composition is usually prepared as a liquid composition containing a solvent (dispersion medium). The solvent can be suitably used as long as it disperses or dissolves other components and does not react with the components and has moderate volatility.

Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethyl ether. Glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether An alkyl lactate such as a polyalkylene glycol monoalkyl ether, methyl lactate or ethyl lactate, methanol, ethanol, propanol, butanol, isopropanol, isobutanol, butanol, (cyclo)alkyl alcohols such as octanol, 2-ethylhexanol and cyclohexanol, ketone alcohols such as diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl (poly)alkylene glycol monoalkyl ether acetates such as butyl acetate, 3-methyl-3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol Ketones such as ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers, methyl ketone, 2-heptanone, 3-heptanone, etc., ketones such as cyclopentanone and cyclohexanone , diacetate such as propylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, methyl 3-methoxypropionate, 3-methoxy An alkane such as ethyl propyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate or 3-methyl-3-methoxybutylpropionate Oxycarboxylic acid esters, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, butyrate B Ester, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, 2- Other esters such as ethyl oxobutanoate, aromatic hydrocarbons such as toluene and xylene, N,N-dimethyl Amides, N, N- dimethylacetamide, N- methylpyrrolidinone, etc. Amides or Lactams amines.

The content of the solvent in the composition is not particularly limited. The lower limit of the solid content concentration (the total concentration of each component other than the solvent) in the composition is preferably 5% by mass, and more preferably 10% by mass. On the other hand, the upper limit of the solid content concentration is preferably 50% by mass, and more preferably 40% by mass. When the solid content concentration is within the above range, dispersibility, stability, coatability, and the like are further improved.

(Preparation method) The preparation method of the composition is not particularly limited, and adjustment can be prepared by mixing the respective components. For example, in the case where the composition contains a metal oxide as the [B] infrared shielding agent and [C] a dispersing agent, the following method may be employed: first, a [B] infrared shielding agent, a [C] dispersing agent, and the like are prepared. A dispersion of a solvent is added to the dispersion and the [A] phthalocyanine compound or other components are added and mixed. The dispersion or the composition may also be subjected to a filtration treatment as needed to remove the agglomerates.

<Infrared Shielding Film (I)> The infrared ray shielding film (I) according to the embodiment of the present invention is an infrared ray shielding film for a solid-state imaging device formed of the composition for a solid-state imaging device. In the optical filter for a solid-state imaging device having the infrared ray shielding film (I), even when the type of the organic dye contained is small, both the visible light transmittance and the infrared ray shielding property are excellent. Further, the infrared shielding film (I) is excellent in uniform penetration in the visible light region.

The infrared shielding film (I) is preferably incorporated as a constituent member into the solid-state imaging device. In this case, the infrared shielding film (I) functions as an optical filter (infrared cut filter) in a single form. Since the infrared ray shielding film (I) is incorporated in the solid-state imaging device, a large process margin or the like can be obtained, which is preferable. When the infrared shielding film (I) is incorporated in the solid-state imaging device, the infrared shielding film (I) can be disposed, for example, on the outer surface side of the microlens of the solid-state imaging device, the microlens and the color filter. Between the color filter and the photodiode. The infrared shielding film (I) is preferably laminated between the microlens and the color filter or between the color filter and the photodiode.

The optical filter may be formed by laminating the infrared shielding film (I) on the surface area of the transparent substrate. As the transparent substrate, glass, a transparent resin, or the like can be used. Examples of the transparent resin include polycarbonate, polyester, aromatic polyamine, polyamidimide, and polyimine. The optical filter can also be preferably used as an infrared cut filter or the like in a solid-state image sensor.

A solid-state imaging device including the optical filter is a digital still camera, a mobile phone camera, a digital camera, a personal computer (PC) camera, a surveillance camera, a car camera, a portable information terminal, a computer, Useful for video games, medical equipment, etc.

The infrared shielding film (I) can be formed, for example, by the following method. First, after coating the composition on a support, prebaking is performed to evaporate the solvent to form a coating film. Then, after the coating film is exposed, development is carried out using a developing solution, and the unexposed portion of the coating film is dissolved and removed. Thereafter, by performing post-baking, an infrared shielding film (I) patterned into a predetermined shape can be obtained. In addition, when the composition does not contain the [D] polymerizable compound and the [E] polymerization initiator, the curing treatment such as exposure may not be performed. Further, development processing may not be performed, and in this case, an unpatterned infrared shielding film (I) may be formed.

The transparent substrate, the microlens, the color filter, and the like are suitable as the support to which the composition is applied. The coating may be carried out by a suitable coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method (slit coating method), or a bar coating method.

The conditions for the heat drying of the prebaking are, for example, 70° C. or higher and 110° C. or lower, and 1 minute or longer and 10 minutes or shorter.

Examples of the light source used for the exposure of the coating film include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, or the like, or an argon ion laser. , yttrium aluminum garnet (YAG) laser, XeCl 凖 molecular laser, nitrogen laser and other laser sources. As the exposure light source, an ultraviolet light emitting diode (LED) can also be used. The wavelength is preferably a radiation in a range of 190 nm or more and 450 nm or less. The exposure amount of the radiation is usually about 10 J/m ² or more and about 50,000 J/m ² or less.

As the developer, it is usually an alkaline developer. As the alkaline developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4.0]- is preferable. An aqueous solution of 7-undecene or 1,5-diazabicyclo-[4.3.0]-5-nonene. For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline developing solution. Further, it is usually washed with water after development.

As the development treatment method, a shower development method, a spray development method, a dip development method, a puddle development method, or the like can be applied. The development conditions are about 5 seconds or more and 300 seconds or less at normal temperature.

The conditions for the post-baking are usually 180° C. or higher and 280° C. or lower, and 1 minute or longer and 60 minutes or shorter.

The lower limit of the average film thickness of the infrared ray shielding film (I) formed as described above is usually 0.5 μm, preferably 1 μm. On the other hand, the upper limit of the average film thickness is usually 5 μm, preferably 3 μm. When the average film thickness of the infrared ray shielding film (I) is within the above range, the balance between the visible light transmittance and the infrared ray shielding property is further improved. Further, the preferred visible light transmittance and infrared transmittance of the infrared ray shielding film (I) can be applied to the range of the infrared shielding film (II) to be described later.

<Infrared Masking Film (II)> The infrared shielding film (II) according to one embodiment of the present invention is an infrared shielding film for a solid-state imaging device, which substantially contains only one or two kinds of organic dyes, and satisfies the following (A) ~ (C). (A) The average value of the transmittance in the range of 430 nm or more and 580 nm or less is 75% or more (B) The average value of the transmittance in the range of 700 nm and 900 nm or less is 16.5% or less ( C) The transmittance at a wavelength of 1200 nm is 10% or less

The optical filter for a solid-state imaging device including the infrared shielding film (II) has both good visible light transmittance and infrared shielding properties. Further, since the infrared shielding film (II) contains substantially only one or two kinds of organic dyes, it is easy to prepare and has high productivity. Here, "substantially containing only one or two kinds of organic dyes" means that the content ratio of one or two types of organic dyes in all the organic dyes contained is 90% by mass or more. The content ratio is preferably 99% by mass or more, and more preferably 99.9% by mass or more. The infrared shielding film (II) preferably contains substantially only one organic coloring matter.

The form of the optical filter having the infrared ray shielding film (II), that is, the use form of the infrared ray shielding film (II) is the same as that of the infrared ray shielding film (I).

(A) The lower limit of the average value of the transmittance in the range of 430 nm or more and 580 nm or less is 75%, preferably 78%, more preferably 80%. When the average value of the transmittance is equal to or higher than the lower limit, good visible light transmittance can be exhibited. On the other hand, the upper limit of the average value of the transmittance may be, for example, 95%, 90% or 85%.

(B) The upper limit of the average value of the transmittance in the range of 700 nm and 900 nm or less is 16.5%, preferably 16%, more preferably 15.5%, further preferably 15%, and sometimes even better. 14%. When the average value of the transmittance is equal to or less than the upper limit, good shielding properties of near-infrared rays can be exhibited. On the other hand, the lower limit of the average value may be, for example, 5%, may be 10%, or may be 12%.

The ratio of the average value (S) of the transmittance in the range of 430 nm or more and 580 nm or less to the average value (N) of the transmittance in the range of 700 nm and 900 nm or less (S/N) The lower limit of the ratio is preferably 5, more preferably 5.2. On the other hand, the upper limit of the ratio may be 10 or 8 or 6.5.

(C) The upper limit of the transmittance at a wavelength of 1200 nm is 10%, preferably 8%, more preferably 7%, and still more preferably 6.1%. When the transmittance is equal to or less than the upper limit, good infrared shielding properties can be exhibited. On the other hand, the lower limit of the transmittance may be, for example, 3%, 5% or 5.5%.

In the infrared shielding film (II), it is preferable to satisfy the following (D). (D) The visible light uniform transmittance represented by the following formula is 10% or less The upper limit of the visible light uniform transmittance is more preferably 9%, and still more preferably 8%. When the visible light uniform transmittance is equal to or less than the upper limit, uniformity of visible light transmittance can be achieved, and better visual sensitivity correction or the like can be performed. Further, the lower limit of the uniform transmittance of visible light is not particularly limited, and may be, for example, 1%, 3%, or 5%.

Uniform visible light transmittance = {(average of transmittance in the range of 430 nm or more and 580 nm or less - the lowest value of the transmittance in the range of 430 nm or more and 580 nm or less) / wavelength 430 nm The average value of the transmittance above and below 580 nm} × 100 (%)

The infrared shielding film (II) can be formed, for example, as a composition for a solid-state imaging device according to an embodiment of the present invention. The method of forming the infrared shielding film (II) is also the same as the method described as the method of forming the infrared shielding film (I). Among them, the composition to be used contains substantially one or two organic dyes, and at least the [A] phthalocyanine compound corresponds to an organic dye. In the infrared shielding film (II), the organic dye is preferably a phthalocyanine compound represented by the above formula (1) ([A] phthalocyanine compound).

A preferred embodiment of the composition for a solid-state imaging device for forming the infrared ray shielding film (II) is as described above for the composition for a solid-state imaging device. That is, the infrared shielding film (II) preferably further contains an infrared shielding agent ([B] infrared shielding agent), and the infrared shielding agent is a metal oxide, a copper compound, or a combination thereof. Further, the [B] infrared shielding agent is preferably tungsten oxide. The other preferred embodiment of the infrared shielding film (II) is also the same as the infrared shielding film (I) formed of the composition for a solid-state imaging device.

The infrared shielding film (II) preferably contains a polymer having a crosslinked structure. The polymer having the crosslinked structure is formed by a polymerization (crosslinking) reaction of the [D] polymerizable compound or a polymer having a polymerizable group such as a polymerizable unsaturated bond in a side chain. In other words, the infrared shielding film (II) containing a polymer having a crosslinked structure is a cured film of the composition containing [D] a polymerizable compound or the like and [E] a polymerization initiator. The infrared shielding film (II) is obtained by subjecting the coating film of the composition to radiation treatment such as irradiation or heating. The infrared shielding film (II) can exhibit good hardness, heat resistance, and the like, for example, compared with a melt-molded film. Further, the infrared shielding film (II) also has an advantage that it can be easily obtained as a cured film of any shape patterned through a mask or the like.

<Solid-State Imaging Device> The solid-state imaging device according to the embodiment of the present invention is a solid-state imaging device including the infrared shielding film (I) or the infrared shielding film (II). In the case of the solid-state imaging device, even when the type of the organic dye contained is small, the infrared shielding film having both good visible light transmittance and infrared shielding property is provided. Therefore, good visibility sensitivity correction is performed.

The solid-state imaging device generally has a structure in which a layer in which a plurality of photodiodes are arranged, a color filter, and microlenses are laminated in this order. In addition, a planarization layer may be provided between the layers. Light is incident from the microlens side in the solid-state imaging element. The incident light penetrates the microlens and the color filter to reach the photodiode. Further, in the color filter, for example, each of the filters of R (red), G (green), and B (blue) is configured to penetrate light of only a specific wavelength range.

In the solid-state imaging device, the infrared shielding film (I) or the infrared shielding film (II) may be disposed on an outer surface side of the microlens, between the microlens and the color filter, The color filter is interposed between the layer in which the plurality of photodiodes are disposed, and the like. The infrared shielding film (I) or the infrared shielding film (II) is preferably laminated between the microlens and the color filter or between the color filter and the photodiode. Further, another layer (a planarization layer or the like) may be further provided between the infrared shielding film (I) or the infrared shielding film (II) and a microlens, a color filter, a photodiode or the like.

Specific examples of the solid-state imaging device include a CCD, a CMOS, and the like as a camera module. The solid-state imaging device is useful for a digital still camera, a mobile phone camera, a digital camera, a PC camera, a surveillance camera, a car camera, a portable information terminal, a computer, a video game, a medical device, and the like. [Examples]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the examples.

<Synthesis Example 1> A phthalocyanine compound (A-1) represented by the following formula (maximum absorption wavelength: 735 nm) was synthesized according to the above Scheme 1. As a starting material, 1,2-dicyano-3,6-bis(4-methoxybutyl)benzene was used. As the "1. base", lithium pentaerythritol (solid lithium and pentane-1-ol) was used, and as "2. Acid", glacial acetic acid was used. Further, as a salt which provides M ²⁺ , a vanadyl salt is used.

[Chemical 4]

<Synthesis Example 2> The phthalocyanine compound (a-1) represented by the following formula was synthesized by the method described in paragraphs [0020] to [0025] (Example 1) of JP-A-2005-25177 (maximum) Absorption wavelength 692 nm).

[Chemical 5]

<Synthesis Example 3> The phthalocyanine compound (a-2) represented by the following formula was synthesized by the method described in the paragraph [0075] (Example 4) of JP-A-2016-204536 (maximum absorption wavelength 728) Nm).

[Chemical 6]

Other than this, the coloring matter used is as follows. ·Compound (a-3): "FDN-002" of Yamada Chemical Industry Co., Ltd. (phthalocyanine compound: maximum absorption wavelength 807 nm)

<Synthesis Example 4> A tungsten ruthenium oxide (Cs _0.33 WO ₃ ) powder was synthesized by the method described in paragraph [0113] of Japanese Patent No. 4096205.

[Preparation Example] 25.00 parts by mass of the tungsten oxide crucible and "BYK-LPM6919" of BYK-Chemie Co., Ltd. as a dispersing agent (solid content concentration 61% by mass, amine price 120 mgKOH/) g) 13.11 parts by mass and 61.89 parts by mass of cyclopentanone (CPN) as a solvent (dispersion medium). These were filled in a container together with 2000 parts by mass of zirconium oxide particles having a diameter of 0.1 mm, and dispersed by a coating shaker, whereby a dispersion having an average particle diameter (D50) of 19 nm was obtained. Further, the average particle diameter was measured by a light scattering measuring device ("ALV-5000" from ALV, Germany) by a dynamic light scattering (DLS) method.

[Example 1] 50.00 parts by mass of the dispersion and 0.75 parts by mass of the phthalocyanine compound (A-1) and the "KAYARAD DPHA" of the Japanese chemical company as a polymerizable compound were weighed in a container. (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 7.01 parts by mass of "NCI-930" (O-acetamido oxime compound) of the ADEKA company as a polymerization initiator 0.70 mass 0.02 parts by mass of "FTX-218D" (fluorine-based surfactant) of NEOS Co., Ltd. as a surfactant, and "Irganox 1010" (phenol) of BASF Corporation as an antioxidant 0.01 parts by mass of the antioxidant) and 41.50 parts by mass of cyclopentanone (CNP) as a solvent were mixed by a stirrer. The mixture of Example 1 was obtained by pressure-filtering 200 mL of the mixture at 0.5 MPa for 3 minutes using a 0.5 μm polytetrafluoroethylene (PTFE) filter.

[Examples 2 to 3, Comparative Example 1 to Comparative Example 3] Examples 2 to 3 and Comparative Example 1 were obtained in the same manner as in Example 1 except that the composition of each component was as shown in Table 1. Each composition of Comparative Example 3 was used.

[Evaluation] The following evaluations were carried out using each of the obtained compositions. The evaluation results are shown in Table 1.

Each composition was applied by a spin coating method so as to have a predetermined film thickness on a glass substrate. Thereafter, the coating film was heated at 100 ° C for 120 seconds, and exposed to 1000 mJ/cm ² by an i-ray stepper. Then, an infrared shielding film having an average film thickness of 1.4 μm to 1.6 μm was formed on the glass substrate by heating at 220 ° C for 300 seconds. The average film thickness is shown in Table 1. Further, the film thickness was measured by a stylus type step meter ("α step (Step) IQ" of Daiwa Scientific Co., Ltd.). Next, the transmittance in each wavelength region of the infrared shielding film produced on the glass substrate was measured by a glass substrate using a spectrophotometer ("V-7300" of JASCO Corporation). Based on the obtained spectrum, evaluation was performed by the evaluation criteria described below. In addition, the penetration spectrum of the infrared shielding film of Example 1 is shown in FIG. Further, in the penetration spectrum of Fig. 1, the horizontal axis represents the wavelength (nm), and the vertical axis represents the transmittance (%).

(Visible light transmittance) The average transmittance at 430 nm to 580 nm was calculated. When the average transmittance is less than 70%, the sensitivity when used as an infrared shielding film is lowered. Further, regarding the average transmittance, the evaluation was performed using the following criteria. A: 80% or more B: 70% or more and less than 80% C: less than 70%

(Infrared shielding property 1) The average transmittance from 700 nm to 900 nm was calculated. When the average transmittance is 20% or more, the amount of noise increases when used as an infrared shielding film. Further, regarding the average transmittance, the evaluation was performed using the following criteria. A: less than 15% B: 15% or more and less than 20% C: 20% or more

(Infrared ray shielding property 2) Regarding the transmittance at a wavelength of 1200 nm, it can be said that the penetration property is less than 15% and it exhibits practically good infrared shielding properties. Regarding the transmittance at a wavelength of 1200 nm, the evaluation was performed using the following criteria. A: less than 10% B: 10% or more and less than 15% C: 15% or more

(S/N ratio) Obtain the ratio of the average transmittance (S) of the visible light region (430 nm to 580 nm) to the average transmittance (N) of the infrared region (700 nm to 900 nm) (S/N) Ratio), speculation on practical performance. The higher the value of the S/N ratio, the better the performance, and when it is 5 or more, it is judged to be a practical level and can be used. Regarding the S/N ratio, the evaluation was performed using the following criteria. A: 5 or more B: Less than 5

(Visible visible light transmittance) According to the average transmittance (S) of the visible light region (430 nm - 580 nm) and the lowest transmittance (S _min ) of the visible light region, X is obtained based on the following formula (Visible visible transmittance), evaluating the uniform penetration of visible light. X = ((SS _min ) / S) × 100 (%) It can be judged that the smaller the X, the higher the uniform penetration of visible light. Regarding the X, the evaluation was performed using the following criteria. A: less than 10% B: 10% or more

[Table 1]

As shown in Table 1, the infrared shielding films of Examples 1 to 3 were excellent in visible light transmittance and infrared shielding properties (A or B), and were excellent in uniform transmittance of visible light. Further, in the infrared shielding films of Examples 1 to 3, it is understood that the organic dye is only one type or two types, but the above-described excellent characteristics can be exhibited. [Industrial availability]

The composition for a solid-state image sensor of the present invention can be preferably used as a material for forming an optical filter of a solid-state image sensor, more specifically, an infrared filter or the like.

no

1 is a transmission spectrum of an infrared shielding film of Example 1.

Claims (14)

A composition for a solid-state image sensor comprising a phthalocyanine compound represented by the following formula (1); In the formula (1), a plurality of R are each independently an alkyl group or an aryl group; and a plurality of X are each independently a hydrogen atom, a halogen atom or an alkyl group; and a plurality of X may be bonded to each other and bonded thereto. The carbon chains together form an aromatic ring; M is a derivative of two hydrogen atoms, a divalent metal atom or a trivalent or tetravalent metal atom; and a plurality of n are each independently an integer of from 3 to 6. The composition for a solid-state imaging device according to the first aspect of the invention, further comprising an infrared shielding agent, wherein the infrared shielding agent is a metal oxide, a copper compound (other than the phthalocyanine compound), or a combination thereof. The composition for a solid-state imaging device according to claim 2, wherein the infrared shielding agent is tungsten oxide. The composition for a solid-state imaging device according to the second aspect of the invention, wherein the content of the metal oxide, the copper compound or the combination thereof is 1% by mass or more and 70% based on the total solid content. Below mass%. The composition for a solid-state imaging device according to any one of the first to fourth aspects, wherein the content of the phthalocyanine compound is 0.1% by mass or more and 30% by mass or less based on the total solid content. The composition for a solid-state imaging device according to any one of the first aspect, wherein R in the formula (1) is a linear or branched alkane having 1 to 12 carbon atoms. base. The composition for a solid-state imaging device according to any one of the above-mentioned claims, wherein M in the formula (1) is H ₂ , Pd, Cu, Zn, Pt, Ni, Co. , Fe, Mn, Sn, In, SnCl ₂ , AlCl, VO or TiO. An infrared ray shielding film for a solid-state imaging device, which is formed by the composition for a solid-state imaging device according to any one of the first to seventh aspects of the invention. An infrared shielding film for a solid-state imaging device, which substantially contains only one or two kinds of organic dyes, and satisfies the following (A) to (C), and (A) penetration in a range of 430 nm or more and 580 nm or less The average value of the rate is 75% or more. (B) The average value of the transmittance in the range of 700 nm or more and 900 nm or less is 16.5% or less (C) The transmittance at a wavelength of 1200 nm is 10% or less. The infrared shielding film according to claim 9, wherein (D) the visible light uniform transmittance represented by the following formula is 10% or less, and the visible light uniform transmittance = {(wavelength 430 nm or more and 580 nm or less). Average of the penetration rate in the range - the lowest value of the transmittance in the range of 430 nm or more and 580 nm or less) / the average of the transmittance in the range of 430 nm or more and 580 nm or less} ×100 (%). The infrared shielding film according to claim 9 or 10, further comprising an infrared shielding agent, wherein the infrared shielding agent is a metal oxide, a copper compound or a combination thereof. The infrared shielding film according to claim 11, wherein the infrared shielding agent is tungsten oxide. The infrared shielding film according to any one of the items 9 to 12, wherein the organic dye is a phthalocyanine compound represented by the following formula (1); In the formula (1), a plurality of R are each independently an alkyl group or an aryl group; and a plurality of X are each independently a hydrogen atom, a halogen atom or an alkyl group; and a plurality of X may be bonded to each other and bonded thereto. The carbon chains together form an aromatic ring; M is two hydrogen atoms, a divalent metal atom or a trivalent or tetravalent metal derivative; and a plurality of n are each independently an integer of from 3 to 6. A solid-state imaging device having the infrared shielding film according to any one of claims 8 to 13.